AbstractOn irradiation on a dry silica gel surface, 2‐(N, N‐dialkylamino)ethyl 3‐benzoylacrylates undergo selective E‐Z isomerization. Competing processes, such as remote‐hydrogen abstraction via a charge‐transfer state, with the photoisomerization in solution are completely suppressed on the surface. The yield of theZ‐ from theE‐ isomer increases with increase in the coverage of theE‐isomer on the surface, reaching a limiting value. Thermal isomerization of theZ‐ to theE‐ isomer occurs easily on the silica gels surface when the alkyl group on the nitrogen atom is small. Benzoylacrylates without any amino group also undergo selecti