We investigated how the Z-scan technique can be explored to distinguish two types of nonlinear refractive effects by employing two distinct laser polarizations. It is possible that pure electronic, molecular orientation and thermal nonlinear effects may occur simultaneously during light-matter interaction. We found a way to discriminate and quantify two distinct nonlinear processes from Z-scan signals measured with linear and circular polarizations. This paper provides analytical equations for nonlinear refractions and in order to test them, we carried out measurements in CS2 and in a rhodamine-B solution, where electronic and orientational, and electronic and thermal nonlinearities mixing, respectively, are present.