Direct leaching with NaOH can be an economically acceptable method for vanadium (V) and tungsten (W) recovery from spent selective catalytic reduction (SCR) catalysts. However, different chemical-physical characteristics of catalysts would affect the V and W leaching. In this paper, the V and W leaching behavior of various sources of SCR catalysts with a local difference (yellow and gray color) were systematically investigated with alkali leaching solution under ambient pressure. Different leaching efficiencies from yellow and gray color areas were correlated with oxidation states and species of V and W on catalyst surfaces, as characterized by X-ray photoelectron spectroscopy (XPS), Raman, Fourier transform infrared spectroscopy (FTIR), and other analytic methods. For the V leaching efficiency, the samples from a gray area of catalysts (40.0–51.0%) were lower than that from the yellow area (66.8–69.8%). The higher molar ratio of V3+ and a lower molar ratio of V5+, and the lower total V content on the surface of the samples from the gray area could be the main reasons for the lower V leaching efficiency. As for the W leaching efficiency, the samples from the gray area (44.6–57.3%) were slightly higher than that from the yellow area (38.0–52.6%) of catalysts. The less total W content of surface species and stronger interaction among V–W–Ti of yellow area samples resulted in the lower leaching efficiency. These differential leaching efficiencies needed to be taken into consideration for recovering V and W from spent SCR catalysts.