Interactions of polyvinylpyrrolidone (PVP) with metal chlorides (MgCl 2 , CaCl 2 , KCl and BaCl 2 ) have been investigated by viscometric and spectrophotometric techniques in aqueous solutions. Intrinsic viscosity [η] of (PVP) has shown a discontinuity with varying concentration of metal chlorides. The decreasing order of effectiveness of cation is K 1+ > Ca 2+ > Mg 2+ > Ba 2+ for poly(vinylpyrrolidone) solution. Changes in the absorption spectra of the cosolutes were observed in the presence of PVP in the lower limit of the UV-visible region i.e. 200-210 nm. These changes were attributed to interaction of PVP molecules with the cosolute molecules. As the concentration of the cosolute increased, a red shift in the peaks was observed, indicating an increase in interaction between PVP and cosolutes. Interactions of polyvinylpyrrolidone (PVP) with metal chlorides (MgCl 2, CaCl 2, KCl and BaCl 2) have been investigated by viscometric and spectrophotometric techniques in aqueous solutions. Intrinsic viscosity [η] of (PVP) has shown a discontinuity with varying concentration of The decreasing order of effectiveness of cation is K 1+> Ca 2+> Mg 2+> Ba 2+ for poly (vinylpyrrolidone) solution. Changes in absorption spectra of the cosolutes were observed in the presence of PVP in the Lower limit of the UV-visible region ie 200-210 nm. These changes were attributed to interaction of PVP molecules with the cosolute molecules. a red shift in the peaks was observed, indicating an increase in interaction between PVP and cosolutes.