The invention provides a method of synthesizing methyl acetate through acetylene carbonylation.The method includes: using acetylene, methanol and carbon monoxide as reaction raw materials; under conditions with reaction temperature of 30-80 DEG C and initial pressure of 1,2-6.5 MPa, adopting a palladium-based catalyst immobilized by organic ligand polymer to catalyze acetylene carbonylation to synthesize methyl acetate.2-pyridyldiphenylphosphine (2-PyPPh2) is adopted as an organic ligand and grafted with vinyl to prepare vinyl2-pyridyldiphenylphosphine, cross-linking polymerization is performed under certain conditions to form solid organic ligand polymer (N-PPOL), and the organic ligand polymer is complexed and immobilized with palladium acetate to prepare the palladium-based catalyst immobilized by the organic ligand polymer.Methyl acetate is synthesized through acetylene carbonylation in one step and has high activity, high selectivity and high easiness in separation and recycling.