Photoaddition of various phenoxyacetates to N-methylphthalimide affords the corresponding hydroxyphthalimidines in yields of 21–93%. The diastereoselectivity of the intermolecular addition is studied for a series of 2-substituted phenoxyacetates with low diastereoselectivities being observed. Comparison experiments with anisole and ether-containing phthalimide confirm that the crucial electron-transfer