The St Vincent and Grenadines striker, who famously lead Kedah to a double treble in 2007 and 2008, scored four second half goals following Mohamad Zaquan Adha Abdul Radzak's 49th minute opener at the Stadium Sultan Ibrahim in Muar.
James' impressive haul comes hot on the heels of the brace he notched for ATM when they downed NS Betaria FC to win their season opener.
Elsewhere, Pos Malaysia eased past Majlis Perbandaran Muar 4-0 at the Stadium Majlis Perbandaran Selayang (MPS) thanks to G.Puaneswaran's brace as well as strikes from goals from S.Sumindran and Muhammad Fakhrul Aiman.
At the Bukit Jalil Stadium, Pahang defeated Harimau Muda B 4-0, and in Paroi, Police beat USM FC 2-0.
Newcomers Negeri Sembilan Betaria drew 1-1 with Johor FA, while Perlis lost 2-1 to Sime Darby.