There are so many opening themes in RPGs, i'm not sure where to even start while limiting myself to just a few
Nonetheless, I'll do my best with some shout-outs.
Xenoblade X
Ar Tonelico
Tales of the Abyss
Ys Origin
Trails in the Sky the 3rd
And for variety's sake some western RPG ones (AKA the Jeremy Soule section):
Morrowind, because yes, it does deserve more credit than the Skyrim version
Guild Wars: Eye of the North
Guild Wars 2