In the EO tradition it is attributed to the 5th Century (just a decade or so before Chalcedon) in Constantinople - I think during Patriarch Proclus's time. By the time Chalcedon was convened, it was in use and accepted (I think it made it into the acts of the Council).
Suryoyutho : I should point out, in case you didn't know, that EO and some OO seem to view the hymn has having a different focus. From my (limited) exposure, for many OO (Syriac and Armenian; I'm not sure about Coptic and Ethiopian and Indian) the Trisagion is in reference to Incarnate Son of God, while to the EO it is in reference to the Trinity (which is why the EO don't use the "who was crucified for us" language).
As for evidence of historical use: besides the Acts of Chalcedon, there is also reference in the life of St. Savvas the Sanctified (who was a Palestinian monk, father of the EO Typikon, and a defender of Chalcedon in the Palestinian monastic communities) to a certain group of Armenian monks who wanted to join his monastery, and he allowed them to have their own space and to celebrate services in their own language (without translation). However, when he heard that their "Holy God" was longer than what he was accustomed to he investigated, and when he heard the extra phrasing he insisted that only that hymn would be sung in Greek rather than Armenian.
(The above is not presented in a spirit of "Who is right," but rather a historical footnote providing a timeline of use; by the late 5th century the hymn was already used, and in fact sung differently by EO and OO.)