Rouse will join Save the Children in September as head of its corporate partnerships division.
He was appointed as the BHF's head of corporate partnerships in 2002, and oversaw a dramatic increase in the charity's corporate income as well as securing partnerships with companies such as Lloyds TSB and the Home Retail Group, which owns Argos and Homebase.
Caroline Underwood, director of philanthropy and partnerships at Save the Children, welcomed Rouse's recruitment.
"This appointment signals an exciting development in Save the Children's corporate partnership activities and we are determined that 2010 will see these partnerships continue to expand," she said.
Save the Children already has partnerships with firms including Ikea, Reckitt Benckiser and British Gas.