Enamides are versatile precursors for synthesizing bioactive compounds. As their alkylations often require perstoichiometric amounts of oxidants, transition metals, or photocatalysts, we herein report a simple alternative for their alkylations by just using visible light to irradiate the mixture of the readily available N-hydroxyphthalimide esters and enamides without an additive. The reaction involves the photoactivation of a π-π stacking EDA complex between the substrates.