The concept of the "Twelve Gods" is older than any extant Greek or Roman sources, and is likely of Anatolian origin. The gods meet in council in the Homeric epics, but the first ancient reference to religious ceremonies for the Olympians collectively is found in the Homeric Hymn to Hermes. The Greek cult of the Twelve Olympians can be traced to 6th-century BC Athens and probably has no precedent in the Mycenaean period. The altar to the Twelve Olympians at Athens is usually dated to the archonship of the younger Pesistratos, in 522/521 BC.
There was some variation as to which deities were included, but the canonical twelve as commonly portrayed in art and poetry were :
Zeus Poseidon Hades Hestia Hera Ares Athena
Apollo Aphrodite Hermes Artemis Hephaestus
Source: http://en.wikipedia.org/wiki/Twelve_Olympians