It is generally observed that electrical transport properties of simple liquid metal based alloys can be explained well in terms of Faber-Ziman theory, 2k F scattering model and finite mean free path approach. However, these approaches give poor description for materials, which show departure from nearly free electron (NFE) model. Taking Pb-Li as a test case of a system showing departure from NFE (which also exhibit compound formation tendency and disparate mass system), a new technique is proposed to compute electrical transport properties using model potential formalism coupled with t-matrix formulation. We have treated valence number of Pb & Li as a parameter in determining phase shifts. Further, rather than calculating phase shift in terms of Muffin-Tin potential, we have used model potential formalism. Present results suggest that compared to other three theoretical approaches mentioned above, present coupling scheme reproduce qualitative features of electrical transport properties of liquid Pb-Li alloys, which can be used further to study electrical transport properties of similar systems.