The zinc-base plated steel sheet has a steel sheet, a zinc-base plating layer on the steel sheet, and a composite coating film formed on the plating layer, which composite coating layer contains a P ingredient, an N ingredient, and at least one element selected from the group consisting of Mg, Al, Ca, Ti, Fe, Co, Ni, Cu, and Mo, and is prepared by applying an aqueous solution containing a cationic ingredient (α) and a phosphoric acid ingredient (β) onto the surface of plating layer on the zinc-base plated steel sheet, and then drying the applied aqueous solution, without giving washing with water, and which cationic ingredient (α) consists essentially of at least one metallic ion selected from the group consisting of Mg, Al, Ca, Ti, Fe, Co, Ni, Cu, Mo, and NH4+ ions.