The rheological properties of aqueous solutions of poly(methyl vinyl ether-co-maleic anhydride) (PMVE-MA) upon addition of metallic cations at different pH values were investigated. Sol-gel transition and shearthickening phenomena at moderate shear rate were observed upon increasing the amount of metallic cations, especially for cupric cation. At certain molar ratio (f gel ) of added cupric cations to carboxyl groups in PMVE-MA, the system became gel-like, and the storage modulus (G′) and loss modulus (G′′) were parallel and exhibited a power-law dependence on the frequency, which is consistent with Winter's hypothesis of determining the gel point of a crosslinking system. The shear-thickening behavior depends on f gel , pH, metallic valence, and temperature.