Apollo didn't have any solar properties in Homeric times, and he and Helios were clearly distinct entities. Helios is extensively discussed in Book XII of the Odyssey, for example.
From the 5th century BCE and onwards Helios started to be identified with Apollo. An early reference to the fusion of the two beings can be found in fragment 781 of Euripidis' Faethon, where the poet tells us that Helios is "rightly called Apollo":
> ὦ καλλιφεγγὲς Ἥλι᾿, ὥς μ᾿ ἀπώλεσας καὶ τόνδ᾿ Ἀπόλλων δ᾿ ἐν βροτοῖς ὀρθῶς καλῇ, ὅστις τὰ σιγῶντ᾿ ἀνόματ᾿ οἶδε δαιμόνων.
The association became a lot more commonplace during Hellenistic times.