The invention discloses a method for surface modification of a hydrophobic polymer microporous membrane. The method comprises the steps of dissolving a pyrocatechol compound and a polyamine molecule in a solvent, and adjusting the mixture to be alkaline so as to obtain a modification solution; soaking the hydrophobic polymer microporous membrane in the modification solution to realize the surface modification of the hydrophobic polymer microporous membrane through reaction, wherein the structural formula of the pyrocatechol compound is shown by a formula I, and in the formula I, R is H, -CH3, -(CH2)nCOOH, -CHO or OH and n is an integer between 0 and 2. The microporous membrane modified by the method disclosed by the invention can be applied in the fields of diaphragms of positive and negative materials of lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, polymer batteries and the like, as well as separation membranes including reverse osmose membranes, micro-filtration membranes, nano-filtration membranes, ultrafiltration membranes, electrodialysis membranes, gas separation membranes and the like to improve the performances of materials and devices.