Ion-exchange processes in potassium titanyl phosphate (KTiOPO4 or KTP) single crystal immersed in Rb, Rb–Ba, Rb–Sr nitrate molten solutions have been investigated by using Rutherford backscattering depth-profile analysis. The depth to which Rb-ion exchange occurred in KTP was found to be sensitive to the presence of as little as 0.1% of a Ba impurity in a molten solution of rubidium nitrate. The addition of impurities such as Ba significantly increased the ion-exchange depth of Rb in KTP, and the Rb distribution after ion exchange. Using pure RbNO3, however, the depth of the Rb ion exchange was relatively shallow, and the Rb surface concentration was measurably greater at the minus than at the plus polar-axis faces of the crystal. These findings are relevant to the application of ion-exchange techniques to the fabrication of optical waveguides on KTP substrates. © 1997 American Institute of Physics.