Okay this ship is a tad tough to propaganda for given that it's not completely headcanon but also not completely canon. Some of this stuff is just kinda inferred because these two don't ever really interact? Catherine just talks about Rhea a lot and Rhea doesn't really talk about or interact with Catherine much. I've shipped with less though!
Let's start with basics. They're both arguably bisexual. Rhea can enter a marriage with either gender of byleth, and Catherine has multiple romantic endings with men while simultaneously being in love with Rhea.
Multiple of Catherine's endings, even when she's married to someone else, have her leaving the church and retiring to Zanado with Rhea. She has one ending where she stays at the church, at that's with Byleth who has avatar privilege. Without Rhea, she pretty much always starts traveling the world. Rhea is the only reason she stays at the church.
In her S support with Byleth that she's a servant of Rhea, not the church. Whether Rhea is alive or not, she admits she's lost. Rhea means the world to her to say the least. This is because when Catherine was a student, her life was saved by Rhea. She was nearly killed by monsters, and Rhea took her "muddied, bloodied body into her arms (Byleth A support, 2019)…" She saved her life again after Rhea took her in once she had to flee Faerghus, thanks to a false regicide accusation. It's pretty clear why Catherine loves Rhea.
Her death quote asks Byleth to save her. She has an advice box where she mentions she's getting used to her absence, and hates it. She's assumes that Rhea doesn't feel nearly as strongly, as shown in her explore dialogue where she sadly says "Lady Rhea's not waiting for me, I know, no matter how much I might wish she were. She's waiting for you (Byleth) (Explore Chapter 21 AM, 2019)." Despite this for better or worse, she's still devoted to her. The only thing she refuses to do for her is die, which I'm not sure if she ever elaborates on. I assume it's because if she did, she couldn't serve her anymore.
Let's talk from Rhea's perspective. Rhea is said to be very lonely despite being surrounded by her followers. She also says she has no friends she can fully trust. Thanks to her past, she keeps everyone at arm's length. That doesn't mean she doesn't care about them. She also says she'd love to have lunch with the students, but is scared of being a bother. She's a lot more socially awkward than she seems.
So to have someone who has so much undying faith in her most likely means a lot. Rhea is probably aware of Catherine's crush, but she may be unaware of how deep it goes. Or she believes that if Catherine knew the truth, she'd abandon her considering that Rhea does have issues with that. It's a shame that the route that truly shows Catherine's loyalty, Crimson Flower, Rhea is beyond the point of really caring about what others think of her.
When Catherine finds out about the Immaculate one, she isn't horrified. She isn't upset. Her only concern is ending her love's suffering. Rhea needs someone who really and truly has her back, who won't judge her, and Catherine does.
Rhea's kindness and patience is something that Catherine needs in a partner. Catherine doesn't seem to think too highly of herself, she just puts her faith in Rhea. Rhea clearly trusts Catherine given that she lets her use a relic, aka one of her dead people, despite that Catherine doesn't really believe in the seiros faith. I feel Rhea does think highly of Catherine, but again she keeps everyone at arm's length. When they retreat to Zanado, Rhea can let her hair down and truly show how much she means to her.
Again much of this is headcanon, but most fe ships are. I think these two have a lot more potential than they're given credit for to have a fluffy relationship. It doesn't have to be toxic or one sided. Rhea clearly appreciates Catherine, it's just how far it goes that is up for debate. I do wish we got to hear more of how Rhea feels about Catherine, but that's what fanon is for. These two are super sweet in my opinion, and if we ever return to Fodlan I hope we can see more interactions between them. Also butch x femme dynamic slaps.
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