He Married Sophia Hardwicke in London on 30 October 1804, then left England in the Experiment arriving in Australia in June 1805.

Riley acquired a farm at the Hawkesbury in August 1805 then became storekeeper and magistrate for Port Dalrymple, where his two sisters lived with their families.

It was here that Riley became devoted to his land grant at Liverpool, named Raby, after his mother's family, and his love of sheep began.

He developed a trading relationship with his brother Edward Riley, who lived in Calcutta, India, at the time as well as W.S.Davidson in Canton.

In 1819 Riley joined the successful and highly respected firm Donaldson, Wilkinson & Co who were agents for the colonial trade.