The invention particularly relates to pulverized fuel ash-based composite co-polymer concrete and a preparation method thereof, and belongs to the technical field of construction materials. N-methylacetamide/butyl acrylate/methyl methacrylate/propylene copolymer latex is adopted, and the composite copolymer latex is high in compressive strength, has relatively high activity, and can remarkably improve the concrete strength; alkylphenol ethoxylate is used as a co-emulsifier, so that the stability of the N-methylacetamide/butyl acrylate/methyl methacrylate/propylene copolymer latex can be improved; and compared with common copolymer concrete, the pulverized fuel ash-based composite co-polymer concrete is rapid in hardening and high in strength, and is remarkably improved in anti-permeabilityperformance, corrosion resistance and wear resistance, and solves the technical problems that in the prior art, copolymer latex of polymer concrete is relatively single, and is easy to crack when meeting in cold severe weather, and self shrinkage and drying shrinkage caused by hydration, condensation and hardening of concrete are serious.