In Unwanted Harem shows, the last girl to show or confess her feelings for the lead is the one with the best chance of winning him.
Usually they will look like the least compatible couple in the beginning; she will only warm up to him later in the series.
This law is especially likely to hold if the girl who will be last to confess is a Type A Tsundere.
Note that it's the last confession that wins. This rule and First Girl Wins can hold at the same time, and it is entirely possible that everyone else will notice her love before she can admit it.
Corollary: The girl who states her attraction to the lead from the get-go stands next-to-no chance of winning the guy.
The reason for this is simple. The girl in question is the one whom the protagonist will love back after the confession, the other half of the Official Couple. Once the official couple is truly official, the premise for the Unwanted Harem show is gone. Thus, her confession will be the last for the same reason people always find lost items in the last place they look: after that, there's no longer any need to look.
Be warned before you proceed: "Winning", in this sense, tends to be spoilerific.
- Ranma ½ is a classic example with Ranma and Akane... Although technically, Akane has never actually confessed that she likes him. (It's pretty damn obvious though.) Ranma is the only one who has officially confessed out of the two of them (He denied it pretty quickly afterwards, but hey, it counts!), so this example is inverted.
- The same goes for Love Hina with Keitaro and Naru
- The Corollary is painfully demonstrated in the Da Capo II anime - Koko confesses her feelings to Yoshiyuki at the end of the first episode. While he accepts and they go out for awhile, their relationship is rather strained, and eventually they break up at the end.
- In the ShuffleShuffle anime, it is played straight with Asa and Rin.
- Ai Kora has Sakurako announce her love last. In fact, she doesn't confess until a little over halfway through the very last chapter of the series, even though Maeda had confessed his love (several times in one day!) in an earlier chapter.
- Subverted and inverted in Naruto.
- Subversion: Naruto is given two love confessions. The first one is from Hinata, an Anguished Declaration of Love that would have turned into a Dying one if not for Sakura saving Hinata's life. The second is from Sakura herself -- but it turns out to be a fake one, which she makes in a desperate attempt to break off the promise he made to her years ago to bring Sasuke back. Naruto immediately sees through Sakura and refuses her confession, even calling her out for lying about her feelings for him, and nailing the coffin on the Naruto/Sakura ship. In The Last, Naruto confesses twice to Hinata - she rejects his first confession because she was in the middle of a plan to save her sister from the Big Bad who also doubles as her Stalker with a Crush, but accepts the second one and they're later Happily Married with two kids (and in Boruto, an adoptive one).
- Inversion: Sasuke had already given an Anguished Declaration of Love to Sasuke, trying to keep him from defecting from Konoha. Sasuke thanks her - but knocks her out and then defects anyway. Several years later, he returns to Konoha and they get together with a daughter, but their relationship's quite rocky for some time.
- In Super Dimension Fortress Macross, Misa Hayase is promoted to becoming captain of her own ship. Realizing that she may not see Hikaru Ichijou ever again, she gives him one of these - even when he and Lynn Minmay are, by that point, more or less in a relationship from quite a while ago. Hikaru is genuinely shocked, has a Love Epiphany and runs after her. Minmay sees this and also has a realization - that not only she knew Hikaru's heart was with Misa rather than her, but she refused to admit it and kept pushing for said relationship between the two. She then tells this to Hikaru and encourages him to go for Misa anyway, and the two get together under the snow.
- In the Sorcerer Hunters manga, Chocolat and Tira confess their love for Carrot when they become uneasy about his relationship with a girl named Mousse. Chocolat, being the bolder one, confesses first, while Tira gets a double-page spread as she confesses next. In the final volume, Carrot marries Tira.