It was around this time that Pember became associated with N.N. Football Club, which played on fields opposite his house. Both Arthur and his younger brother George are recorded playing for N.N. in a victory over Barnes F.C. in April 1863. Pember represented N.N. as club captain at the first meeting of the Football Association (FA) on 26 October 1863. This meeting began with Pember being "requested to take the chair", and ended with him being formally elected the Association's first president.According to C. W. Alcock, Pember was "the moving formation" in the formation of the FA:
