He was one of few allies of Xena's, during the Twilight of the Gods. He helped to protect Eve from the Olympians and later raised her when Xena and Gabrielle were contained in ice for 25 years. He and Eve (now with the alias of "Livia") were to be married and she was to become the Empress of Rome, but her affair with Ares was exposed when Xena returned and the marriage was called off. He then allowed some of his troops to help Xena bring down Livia and the renegade Romans.
Octavius was adopted by Julius Caesar (his great-uncle) and raised as his son. He was then next in line to rule Rome, after Caesar.
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After Ares took Xena and Gabrielle away, he took it upon himself to raise Eve as his own. He sent her away as a child and was raised to fight like a Roman from an early age. Octavius then worked his way through the political ladder, until he eventually became Emperor. He then adopted his predecessor's middle name, Augustus, as well as began his reign.
Whilst Eve was growing up, Octavius gave her the name Livia, to protect her true identity from the Olympian gods, a name that would later strike fear in the hearts of the most feared warriors. Ares, God of War, befriended Livia and started an affair with her. He then told her that, in order to become Empress of Rome, she had to marry Octavius. She's about to, but when Xena returns and reveals that she has been having an affair with Ares, he calls off the wedding and ruled Rome alone.
Augustus was replaced by Tiberius at some point during Twilight, but his actual fate is never addressed.