A distillation apparatus for subjecting a crude readily polymerizable compound to distillation under vacuum conditions to purify it, the distillation apparatus having a distillation column and a vacuum generator and an exhaust gas conduit of the vacuum generator connected to a connecting conduit therebetween through a pressure control valve. A method provides purifying of a readily polymerizable compound by subjecting a crude readily polymerizable compound to distillation under vacuum conditions to purify it, the method including using a distillation apparatus having a distillation column and a vacuum generator and an exhaust gas conduit of the vacuum generator connected to a connecting conduit therebetween through a pressure control valve and controlling the action of the pressure control valve based on a pressure of the distillation column.