A series of polar group functionalized polystyrene-supported phosphine reagents were examined as catalysts in the aza-Morita–Baylis–Hillman reactions of N-tosyl arylimines and a variety of Michael acceptors with the aim of identifying the optimal polymer/solvent combination. For these reactions JandaJel-PPh 3 (1mmol PPh 3 /g loading) resin containing methoxy groups (JJ-OMe-PPh 3 ) on the polystyrene backbone in THF solvent provided the highest yield of all the catalyst/solvent combinations examined. The methyl ether groups were incorporated into JJ-OMe-PPh 3 using commercially available 4-methoxystyrene, and thus such polar polystyrene resins are easily accessible and should find utility as nucleophilic catalyst supports.