 If you liked
Junjou Romantica
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 ...then you might like
Empty Heart: Itsuwari no Koi Dakara
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I actually just realized this after I finished Empty Heart. The approach to each story is different, but the way they unfold and carry on are quite similar.
Both seme's in the story are named 'Usami' (though that isn't the half of it). Takumi (the story's uke) is in love with his teacher, Jun Usami. Takumi has an older brother named Ryuuta., who Usami is in love with (mirrored to Usami being in love with Misaki's brother Takahiro in Junjo).
(I'll refer to Junjo's 'Usami' as Usagi now to avoid confusion.)
The approach to both are different. Takumi looks exactly like his brother and seduces Usami into sleeping
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Recommended by StarPebblit
The Romantica pair of Junjo Romantica have a similar sort of beginning to Empty Heart--a main character is in love with his best friend for years, but said best friend doesn't notice and goes on to get married; he then ends up sleeping with said best friend's younger brother and falls in love. The characters themselves, however, have very different personalities, so the relationship dynamic is somewhat different in each story.