The study of electrical resistivity of compound-forming liquid alloy, NaPb, is presented as a function of concentration. Hard sphere diameters of Na and Pb are obtained through the interionic pair potentials evaluated using Troullier and Martinsab initio pseudopotential, which have been used to calculate the partial structure factors S(q). Considering the liquid alloy to be a ternary mixture, Ziman formula, modified for complex formation has been used for calculating resistivity of binary liquid alloys. Form factors are calculated usingab initio pseudopotentials. The results suggest that Ziman formalism, when used withab initio pseudopotentials, are quite successful in explaining the electrical resistivity data of compound-forming binary liquid alloys.