The Langmuir-Blodgett (LB) technique is a way of making supra-molecular assembly in ultrathin films with a controlled layered structure and crystal parameter, which have many envisioned technological applications for optical and molecular electronic devices as well as signal processing and transformation. Probably LB technique is the best method to manipulate materials at molecular level and provides a scope to realize the molecular electronics in reality. In this review article, we have discussed about the general introduction of LB technique and recent development on LB and related system including (i) LB methodology, (ii) characterizations of LB films, (iii) LB films and molecular electronics, (iv) historical review of LB films, (v) research and applications including fundamental research and application towards devices.