We all know that Homura loves Madoka, but in the series she never reciprocated that love. Of course there is a possibility that they became a couple in one of the loops, but unless the authors say so, all we have is insinuation and undertones. That's why I say that KyouMami is the closest we could have to a "canon" pairing, because they were the only ones to have some kind of lasting relationship in the series.