The class of stimuli-responsive molecular bistable materials featuring spin crossover (SCO), single-molecule magnets (SMMs), single-chain magnets (SCMs), and metal-to-metal electron transfer (MMET) properties via spin manipulations in molecular systems show tremendous potential in diverse areas of quantum technologies. These materials show noticeable bistability in magnetic, photo, and electric switchable properties. Among these, SCO materials have been considered the most important and exciting candidates, since they represent an easy and substantial pathway to realize various aspects of modern-day technological applications, which includes molecular and spintronic devices, sensors, switches, data recording, and storage materials. Minute alteration of external perturbations e.g., temperature, pressure, light irradiation, magnetic field, etc. can easily switch the spin-state of these materials in a controlled and reversible manner with notable modifications in inherent properties e.g., chromic, magnetic, conductive, optical, etc. Based on the temperature dependence of magnetic susceptibility, the SCO phenomenon can be demonstrated as gradual, abrupt together with or without hysteresis, stepwise, and incomplete within the measurement frame. This nature of the SCO phenomenon is affected by the absence or presence, nature, and strength of cooperativity within the system. In this aspect, stepwise SCO with two or more steps has gathered great attention as it generates a characteristic ordered intermediate phase allowing an access to additional spin states, which provides a good platform to explore multifunctional materials with new and improved potential applications in information storage. Such stepwise SCO systems may lead to a possible observation of lesser explored bidirectional LIESST effect, where the intermediate state can switch to metastable light-induced HS or a LS state (one different from inherent ground state) leading to a possibility of observing tristability in the system. Generally, stepwise SCO occurs when non-equivalent SCO metal centers in a molecule exhibit spin state switching at different temperatures. While symmetry breaking in molecular structure generates two or more independent SCO centers in the ordered intermediate phase and displays stepwise SCO. Significant effort has been devoted over the last few years by numerous research groups to explore and realize the correlation between SCO and symmetry breaking. Regardless of the critical development, symmetry-breaking SCO remains a rare and fascinating method to realize the fundamental and application features of SCO materials.