We present the Z-scan technique using azimuthal-variant vector beams for characterizing the nonlinear refractive index of an isotropic nonlinear medium. Compared with the conventional Z-scan measurements, the reliability of the vector beam Z-scan is improved because the focused azimuthal-variant vector beam exhibits a uniform-intensity focal ring instead of a focal spot. Experimentally, our investigation demonstrates that the Z-scan using radially polarized beams is a preferable technique for characterizing the optical nonlinearity of an imperfect sample.