An environmentally benign Chennat‐type synthesis of 4‐aryl‐1,4‐dihydropyridine‐3,5‐dicarboxylic acid dimethyl esters was achieved by heating aldehyde, methyl propiolate and an amine salt in water. Excess amine salt accelerated the reaction, while stoichiometric amounts of reagents resulted in lower yield. Various 1,4‐dihydropyridine (1,4‐DHP) derivatives, some of which would be difficult to synthesize in organic solvents, could be obtained in up to 74 % isolated yield. The reaction utilizes a hydrogen‐bonding network with water to accelerate hydroxyl group elimination from the reaction intermediate. Free amine and protons in water might be act as a nucleophile and electrophilic catalyst, respectively.