In a novel method of homo- or copolymerization of vinyl chloride, a specified coating agent is applied on the surfaces of the portions which will become into contact with the vinyl chloride monomer during the polymerization process. The coating agent is in a form of an aqueous solution of a modified condensation product of phenol and aldehyde, the pH of the solution being adjusted in a range that the product is dissolved at an ambient temperature upon coating of the solution and separates out of the solution upon being heated on the surfaces. The wall surface of the polymerization tank and the like is then coated with a thin film of the coating agent having a uniform thickness and being strongly adhered to the wall surface, thereby providing an excellent effect of preventing adhesion of the product polymer to the wall surface.
