The invention discloses an industrial tail gas liquefaction energy storage power generation system and a power generation method. The system is characterized in that industrial tail gas is subjected to condensation and purification through a tail gas purification heat storage unit; heat energy generated during the condensation and purification process is stored; electric energy is generated from condensed and purified tail gas through a tail gas turbine power generation unit; useful gases like sulfur, carbon, oxygen and nitrogen are liquefied and separated from tail gas output by the tail gas turbine power generation unit through a liquefaction separation storage unit; a pressurization gasification power generation unit drives liquefied useful gases of the liquefaction separation unit to be gasified, and electric energy is further generated; and thereby, industrial tail gas liquefaction, separation, storage and gasification power generation are achieved, the comprehensive utilization rate and emission reduction rate of industrial tail gas are increased, the energy compensation problem of peak regulating and valley filling is efficiently solved, investment of matching generating sets, power transmission and distribution facilities and gas supply networks for building energy storage power stations or peak regulating power stations is reduced, the remote power supply loss and running cost are reduced, and the safety, stability and economy of power supply and peak regulating are improved.