 On the retirement of Sir Alfred Stephen in November 1891, Darley was appointed Lieutenant-Governor of New South Wales, and he administered the government seven times in that capacity.When the position of Governor of New South Wales became vacant in 1901, Serle notes that there were many suggestions that Darley should be given the post, but the post was given to Sir Harry Rawson.Darley's longest period administering the government was from 1 November 1900 to 27 May 1902, a significant period in Australia's political history with the lead up to and the aftermath of federation of the then Australian colonies.