A methanol/MMA azeotrope is broken or avoided by a method comprising the steps of (1) raising the pressure within a first vessel, e.g., a distillation column, that contains a methanol/MMA azeotrope, (2) collecting the azeotrope as a liquid, and then in a second, separate vessel, e.g., another distillation column, (3) raising the pressure sufficiently to allow for the breaking of or avoidance of the azeotrope and the recovery of the methanol.