Philippe made an off-season switch from WA to NSW in a bid to reignite his Sheffield Shield career.
But it's with the white ball that Philippe has made a memorable early impression, with the 27-year-old cracking a career-high 139 off 119 deliveries to lead NSW to 9-287 at Cricket Central on Sunday.
In reply, defending champions WA had a chance to pinch victory after moving to 9-279, needing nine runs off the final eight balls.
But Will Salzmann ended WA's hopes, taking a tough catch at deep point while running backwards and looking into the sun to dismiss AJ Tye.
Salzmann had returned expensive figures of 2-72, but he had the last laugh with the match-winning catch.
Cameron Bancroft top scored for WA with 71, while Ashton Agar (51), Ashton Turner (41) and Hilton Cartwright (41) also produced handy contributions.
Philippe plundered 17 fours and three sixes in his devastating knock, with the star opener particularly brutal with his drives and straight lofts.
WA spinner Ashton Agar suffered plenty of punishment from Philippe on the way to figures of 1-58 from eight overs.
But in a huge positive for WA, paceman Jhye Richardson put his injury woes behind him to finish with 5-63.
Richardson claimed Philippe's wicket in the 38th over courtesy of a brilliant one-handed diving catch from Bancroft at mid-on.
But the damage had already been done, with Philippe's knock helping NSW post a formidable total despite the lack of support around him.
Matthew Gilkes scored 41 off 47 batting at No.7 to be the next best scorer, while tail-ender Tanveer Singh added a handy 26no off 14 balls at the death.
