A Goodreads user asked Sebastien de Castell:

Greatcoats is quickly becoming one of my favorite series, and the characters are also some of my favorite! I am currently halfway through Knight's Shadow, at the part where Falcio meets Ethalia again, but I just can't seem to wrap my head around their romance. Where did it stem from, and why do they have such strong feelings for each other, despite only spending one night together?

This answer contains spoilers… (view spoiler)[Delighted to hear you're enjoying the series thus far!
The third book in the series, Saint's Blood, delves more deeply into Falcio and Ethalia's relationship (and the inherent problems with how that relationship came about.) I'll try to answer your question as best I can without spoiling anything from the next book.

You're absolutely right that it's hard for us, living in a relatively safe world in which we're accustomed to getting to know people before feeling attached and in which "love at first sight" tends to be seen as lacking true depth, to buy into it as easily as Falcio and Ethalia seem to. But remember that these are two people for whom every encounter with another person in the last several years has been fraught with violence or manipulation or sacrifice. Then all of a sudden they connect with someone where none of those things are at play--where it feels almost like starting over again.

More importantly, though, these are two people that see the other for what they represent, rather than who they really are. Ethalia's been enamoured with Falcio since she first saw him at age thirteen when he was the one person who stopped to help her in Rijou. She also sees him as someone she can save (which, thought not a modern notion of the right basis for a relationship, is very much in tune with the path she set herself upon when she joined her order.) To Falcio, Ethalia represents a fundamental 'rightness' that he doesn't see elsewhere. He'd spent years haunted by the madness that had set him off on his path and she was the first person who managed to soothe that away. The things she knows about him, and sees in him, make him feel as if there's this entire life--a different destiny--that he might have had with her. She represents the happiness he might have had if he'd walked a different path.

Finally, and most importantly, Falcio is what's often termed an "unreliable narrator"--he doesn't tell us everything that's really happening but rather how he himself sees it. He mythologizes King Paelis even as others try to point out that the King wasn't as perfect as Falcio remembers. He sees Valiana as reckless and foolish even when the reader can discern that she's neither of those things--and that, in fact, Falcio is often the reckless one. The same is true with Ethalia: he's so desperate to believe that there's still a possibility of a great love in his life that he turns every encounter with her into this destiny-laden moment. It's a flaw they both share and one that may be costly in future...

Hope that helps. Let me know if I haven't fully answered your question!

Regards,

Sebastien (hide spoiler)]

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