Daly, who was the global chief executive of WPP's Maxus media network, has been recruited by Iain Jacob, Starcom's new chief executive for EMEA.
His role will be to work with Jacob on developing the network, taking responsibility for some key markets and its diversification into areas such as digital and content.
Before joining WPP, Daly was the global media development director at Aegis. He was also a media director at Initiative.
Jacob, who plans to build a team of senior executives at European level, said: "Nick has experience at some of the biggest networks."
Daly's appointment coincides with the announcement that Linda Smith will be the next chief executive of Starcom UK. Smith, the commercial director at GCap Media, replaces Jacob and will start her new job on 23 January.