The invention discloses a preparation method of a high-activity waterproof soap-free emulsion polymer. Raw materials for polymerization comprise: 7 to 19 parts of an amide hydrophilic monomer; 6 to 17parts of a soap-free amide hydrophilic monomer; 0.28 to 0.85 part of a chain transfer agent; 0.21 to 0.49 part of an initiator a; 2.3 to 4.5 parts of an initiator b; 9-18 parts of a soap-free alkyl hydrophobic monomer, 202-267 parts of an alkyl hydrophobic monomer, 3.4-7.8 parts of a cross-linking agent, 2.4-6.7 parts of a flexible small monomer, 5-16 parts of a polyether, 0.4-0.9 part of a graphene oxide functional monomer, 3.2-8.6 parts of a pH regulator, 9-20 parts of a neutralizer and the balance of water, wherein the total amount of the raw materials is 1000 parts. According to the invention, amide monomers and alkyl monomers are used as raw materials; soap-free emulsion polymerization method is adopted to obtain a self-made soap-free polymer for water resistance; and the soap-free polymer is reacted with other raw materials to synthesize an emulsion polymer waterproof coating. According to the method, adverse effects caused by emulsifiers are eliminated, graphene oxide is addedto improve the film-forming property and the film-forming strength of the coating, the added cross-linking agent enhances the density and the hardness of formed film, the cohesiveness is enhanced, andthe waterproof capacity and the weather resistance are improved.