 During this time he became associated with the Hume family, explorers and settlers of southern New South Wales.He was schoolmaster to the children of Francis Rawdon Hume (brother of Hamilton Hume) at Rockwood, Appin, and to the family of Hume relative George Barber at Glenrock, Marulan.Riley published several poems dedicated to Hume family members, most notably an elegy for Barber, drowned trying to cross flooded Towrang Creek in a winter storm in 1844, and a lament for John Kennedy Hume, killed in a fight with bushranger Thomas Whitton in the streets of Gunning on 20 January 1840.