The semiconductor PbS polyhedral nanoparticle, synapticula-like PbSe nanorods and PbS/PbSe nanocomposites have been achieved on lead substrates via a one-pot solution method. The lead foil acts not only as the carrier of products, but also as a source of lead. The surfactant of polyvinylpyrrolidone played a crucial role to achieve well-dispersed and uniform products. The EDS analysis and elemental mappings confirmed that all of the elements (S, Se and Pb) were homogeneously distributed throughout the compound samples, and the two components are doped with each other, formed alloyed-type heterostructures. The photoluminescence measurement showed that the three kinds of products possessed unitary blue light emission properties, and the emission peak intensity of PbSe could be improved by doping PbS.