Nonlinear optical (NLO) materials have gained much attention during the last two decades owing to their potentiality in the field of optical data storage, optical information processing, optical switching, and telecommunication. NLO responsive macroscopic devices possess extensive applications in our day to day life. Such devices are considered as assemblies of several macroscopic components designed to achieve specific functions. The extension of this concept to the molecular level forms the basis of molecular devices. In this context, the design of NLO switches, that is, molecules characterized by their ability to alternate between two or more chemical forms displaying contrasts in one of their NLO properties, has motivated many experimental and theoretical works. Thus, this chapter focuses on the rational design of molecular NLO switches based on stimuli and materials with extensive examples reported in the literature. The factors affecting the efficiency of optical switches are discussed. The device fabrication of optical switches and their efficiency based on the optical switch, internal architecture, and substrate materials are described. In the end, applications of switches and future prospectus of designing new molecules with references are suitably discussed.