As for veneration of saints and relics, then anything that worshipped is a god and asking for blessings, intervention in worldly affairs, etc are all acts of worship. So when someone prays to a particular saint seeking something they are engaging a polytheistic act just as one who prays to an idol is engaging in polytheism.
I am not sure about Muslims worshipping Muhammad. Maybe in some polytheistic branches of Islam such as sufism and so forth which were themselves influenced by hindu/christian/etc ideas.