Vayne is currently the only champion with an ability named the same as her title (Night Hunter).
Her given name Shauna is the Irish feminine derivative of Hebrew י(ה)חנון Y(eh)oḥanan "Yahweh is gracious" (cf. Seán), sharing root ḥ-n-n with Annie.
Her surname Vayne comes from Old English fægen "glad" (> var. fain);
This is coincidentally an aristocratic surname in real-life, as the Fanes are earls of Westmorland since 17th century.
As per her retconned lore, Vayne hunts and kills monsters, hybrids, shape-shifters, etc. not due to any ethical guidelines, but to satisfy her bloodlust, making her resemble Dexter Morgan, a fictional serial killer who mostly targets other morally deplorable murderers.
Similarly, Vayne & Dexter both developed killing urge after witnessing their respective parents being murdered (Vayne's father & mother; Dexter's mother).
Vayne was the first champion to always play a quote upon learning an ability (Silver Bolts)