Polyurethane polishing pads are important in chemical mechanical polishing (CMP). Thus, understanding how to decrease the density but increase the porosity is a crucial aspect of improving the efficiency of a polyurethane polishing pad. According to the principle of gas generation by thermal decomposition of sodium bicarbonate and ammonium bicarbonate, polyurethane polishing pad was prepared by a secondary foaming method. The influence of adding such an inorganic foaming agent as an auxiliary foaming agent on the structure, physical properties, and mechanical properties of polyurethane polishing pads was discussed. The results showed that compared with the polyurethane polishing pad without an inorganic foaming agent, the open-pore structure increased, the density decreased, and the porosity and water absorption increased significantly. The highest porosity and material removal rate (MRR) with sodium bicarbonate added was 3.3% higher than those without sodium bicarbonate and 33.8% higher than those without sodium bicarbonate. In addition, the highest porosity and MRR with ammonium bicarbonate were 7.2% higher and 47.8% higher than those without ammonium bicarbonate. Therefore, it was finally concluded that the optimum amount of sodium bicarbonate to be added was 3 wt%, and the optimum amount of ammonium bicarbonate to be added was 1 wt%.