Langmuir Blodgett (LB) process is an important route to the development of organized molecular layered structures of a variety of organic molecules with suitably designed architecture and functionality. LB multilayers have also been used as templates and precursors to develop nano-structured thin films. In this article, studies on the molecular packing and three-dimensional structure of prototypic cadmium arachidate (CdA), zinc arachidate (ZnA) and mixed CdA-ZnA LB multilayers are presented. The formation of semiconducting nano-clusters of CdS, ZnS and Cd_xZn_1−xS alloys within the organic multilayer matrix, using arachidate LB multilayers as precursors is also discussed.