
In the upcoming Dune: Prophecy series several characters from the Dune novels take center stage, while others appear in flashbacks.
While the series may deviate from the source material and indeed introduces its own original characters, it still builds upon the expanded Dune universe. As such, some of the details below might contain spoilers for the series.
Valya Harkonnen, the second Mother Superior of the Sisterhood, has motivations that are both complex and layered. While she genuinely works to stabilize and increase her order's power, she is also driven by vengeance against the Atreides, who played a role in the downfall of House Harkonnen following the Butlerian Jihad - humanity's uprising against its robot overlords.
Valya is a frighteningly powerful woman, in both literal and figurative senses. She trained on Ginaz to become a swordmaster (same as Duncan Idaho), and even before becoming a Reverend Mother, she perfected her use of the Voice.
In her first three years as Mother Superior, Valya began transforming the Sisterhood, renaming it the Bene Gesserit (meaning "well-behaved" in Latin.)

Valya's sister and advisor. One of her claims to fame is murdering Orry Atreides on their wedding night, acting on her sister's orders.
She grapples with the stigma of her family name and the desire to either redeem or leverage it for personal power. Her arc reflects the challenges of overcoming deeply ingrained societal prejudices and the shadow cast by the Harkonnen legacy. This traces back to the betrayal of Abulurd Harkonnen during the Battle of Corrin, which led to the Harkonnens' fall from grace within the Imperium.
Speaking of the Battle of Corrin, it was General Faykan Butler who ascended to the Golden Lion Throne, adopting the name Corrino. Javicco is the great-great-grandchild of Faykan and a direct descendant of the Butler family.
Javicco is mentioned by name in the books, but only as one of the four children of Salvador Corrino, the previous emperor.

Although she will only appear in flashbacks, she remains an immensely important figure in the Sisterhood's history. She was the second Reverend Mother ever - a title that is not given, but earned.
Bene Gesserit undergo a near-death experience to access the memories of all their female ancestors (often referred to as Other Memory) and awaken the full potential of their abilities.
She served as the Truthsayer to Salvador Corrino and founded the orthodox Sisterhood on Salusa Secundus (of Sardaukar fame).
Originally, she was meant to be the co-leader of the Sisterhood with the person who ultimately became her killer: Valya Harkonnen.
Another flashback character, but certainly the most important one.
She was the first Reverend Mother and the founder of the Sisterhood. Raquella was the daughter of Helmina Berto-Anirul, who was the illegitimate daughter of Vorian Atreides, the founder of House Atreides.
This is the same Vorian Atreides whom Valya Harkonnen hates so much, as he was responsible for banishing her great-grandfather, Abulurd Harkonnen to the planet Lankiveil after the Battle of Corrin. (Yes, Vorian lived a very long life.)
Raquella intended for her successors as Reverend Mother Superior to be both her granddaughter Dorotea and her right-hand, Reverend Mother Valya Harkonnen. However, upon Raquella's peaceful death, Valya used the Voice to kill Dorotea, ensuring that leadership of the Sisterhood passed to her alone.
All we know about this character is that he was once a soldier and that he is determined to serve the Imperium by eradicating the Sisterhood.
Me personally, I certainly enjoy Travis Fimmel reprising his role as zealous bearded man with fanatic overtones. He was great doing the same thing in Raised by Wolves, Vikings, Warcraft, etc.

From the official bio we know that she was a formidable royal who united thousands of worlds through her marriage to Emperor Javicco Corrino. She's mother to Ynez and stepmother to Constantine.
She is the responsible heir to the Golden Lion throne, planning to study with the Sisterhood and he is the illegitimate and irresponsible son of the Emperor. Tell me that's not the pitch for the next scifi comedy series.

Officially? The palace swordmaster. Unofficially… well just look at this picture.

What we know from her bio is that she's a strong-willed Fremen woman who serves the royal family while longing for a home planet she's never known.
I'll be interested to see how she got to the palace and how she maintains her Spice addiction.

Once a great love of Emperor Javicco Corrino, her return to the Imperial Opal Palace strained the balance of power in Corrinth City.

The favorite students of Valya and Tula, respectively. Just like their mentors, one of them is confident in her abilities while the other is more introverted and deliberate.

Hope this helped untangle some of the complicated relationships and plot lines.
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