Compositions of HMMM (hexamethoxymethyl melamine)-polyol and acrylate can be cured by a hybrid polymerization composed of free radical polymerization and condensation reaction at high temperature in the presence of an acid. Some synergetic effects were observed, such as enhancement of curing rate, energy compensation, improvement of properties of cured film and formation of interpenetrating polymer network (IPN) in situ. To make the formulation more flexible, some crosslinker-initiators were synthesized. It was found that the use of a latent acid catalyst as the source of acid could increase the shelf-time greatly. On the other hand, acrylate can adjust the viscosity of the formulation and reduce the use of organic solvent. By hybrid polymerization of HMMM-polyol-acrylate, it is promising to formulate a high curing rate, low solvent content, energy conservation and high quality coating.