Blocked high-temperature resistant integrated solvent-free polyurethane resin for leather, and a preparation method and application thereof are disclosed. The polyurethane resin comprises a resin component A and a resin component B. The resin component A comprises a polyether ester polyol-polyisocyanate prepolymer, polyester polyol, a small molecule alcohol chain extender, a foaming agent and a catalyst. The resin component B comprises diisocyanate, polyester polyol and a NCO blocking agent. The blocking agent is one or more selected from phenol, nitrophenol, 2-pyridinol, 3-hydroxyquinoline, triphenylmethanethiol, hexanethiol, dodecanethiol, 3,5-dimethylpyrazole, 1,2,4-triazole, 2-methyl imidazoline, 2-ethyl-4-methylimidazole, caprolactam, N-methylacetamide, phenylacetamide, bisulfate or amine. The polyurethane resin can be used for preparing high-temperature resistance solvent-free polyurethane synthetic leather. The production efficiency is high. Equipment specially used for solvent-free leather synthesis is not needed, operable time is long after product mixing and stability is high.