Nickel (Ni)-Tungsten (W) alloys were electrodeposited galvanostatically (at-10 mA cm(-2)) on copper substrate with 3 different W contents under the controlled hydrodynamic conditions and then the anodic dissolution behaviors of the alloys were observed by potentiodynamic polarization and electrochemical quartz crystal microbalance (EQCM) techniques. While the structure of the electrodeposited Ni-W alloy with low W content (15.90% W) was crystalline, that of the alloy with high W content (50.80% W) was nano-crystalline according to X-ray diffraction patterns. The increase in the W content of the electrodeposited Ni-W alloy resulted decrease at pH 3 and increase at pH 7 and 12.5 in the anodic currents of the alloy. The pH dependent dissolutions caused electrodeposited alloy surface to have W-enrichment at pH 3 and Ni-enrichment at pH 7 and 12.5. These observations indicated that the selective dissolution of Ni or W was the main mechanism in the anodic dissolution of the electrodeposited Ni-W alloys. The EQCM experiments conducted at pH 7 supported the presence of the selective dissolution mechanism that the anodic dissolution potential of W was 0.42 V lower than that of Ni in the electrodeposited Ni-W alloys.