Propylene glycol methyl ether is produced by feeding a solution of a basic catalyst in methanol to a catalytic distillation column containing a heterogeneous basic catalyst defining a heterogeneous reaction zone, and feeding propylene oxide to the column. The methanol reacts with the propylene oxide according to a dual homogeneous catalytic reaction and heterogeneous catalytic reaction to form propylene glycol methyl ether, which is removed from the column as a bottoms product. Alternatively, methanol can be reacted with propylene oxide in a pre-reactor, to form propylene glycol methyl ether, and, when the temperature in the pre-reactor reaches about 100° C., the reaction products are transferred to the catalytic distillation column for further reaction.