Multifunctional materials exhibiting synergistic effects between different physical properties have gained enormous interest in modern research due to their vast potential for device application under practical conditions. The interplay between luminescence and spin crossover is important, as this can help to develop multifunctional materials that interact with light and heat and can be controlled synergically, which allows them to be beneficial for tuning both SCO and Luminescence properties. The usefulness of such systems depends on the extent of synergy between the two properties. The main governing factors are the spectral overlap between the SCO and emission band arising from the luminophore and the conformation and intermolecular interactions between the luminophores. This review presents a concise, up-to-date overview of the multifunctional materials mostly comprising Fe(II) metal center, showing synergistic SCO and luminescence properties covering entire 0D, 1D up to 3D structures with mononuclear to polynuclear systems. However, synergistic SCO and luminescence is even more challenging and thus significantly not explored much. Because even if the quantum efficiency of the luminophores is comparable to that of the acceptors, this synergy depends strongly on the arrangement of the whole molecular network involving intra-and inter-molecular interactions among the metal centers, luminophores and surrounding solvent molecules. Fluorescence emission in these SCOactive complexes can be triggered majorly by two mechanisms: (i) overlap of the fluorophore's emission band and the absorption band of the SCO-active complex, which causes the reabsorption of photons by the HS or LS SCO complexes, and may be the distance between the fluorophore and the SCO center is short resulting that the excited-state energy from fluorophore can be directly transported to the SCO center; (ii) effect of surroundings of the complexes including variations in polarity, vibrational frequency, stiffness can also be used for tuning the fluorescence emission in these complexes. In general, luminophores are grafted onto the ligand backbone to have effective spectral overlap with the SCO center, or the luminophores can show aggregation-induced emission (AIE), which is useful for practical applications. This approach has been implied to develop advanced systems that can work as luminescence thermometry for detecting SCO in such molecular systems. Also, researchers are now-a-days looking for new bifunctional SCOfluorescent complexes where the fluorescence emission originates from lanthanide metal centers or transition metal-organic motifs, which is rare and may exhibit unexpected SCO-fluorescence synergy and energy transfer mechanisms. However, such phenomena are unpredictable, and still, more work is needed to rationalize this synergistic behavior to attain effective multifunctional materials that can be used in optoelectronic and magneto-optical devices. In terms of multifunctional molecules, we have also represented examples of various SCO molecules exhibiting dielectric properties. In many cases, it has been found that magnetic switching and dielectric switching happen in similar temperature ranges, which is a prerequisite for fabricating various sensors or molecular devices. In these cases, the change in magnetic state can be gauged via the dielectric response. From literature, it has been found that 1D-3D molecules show much better changes in the dielectric property as compared to discrete 0D molecules, as in the polymeric structure, the changes are more prominent and thus lead to a large change in the relative permittivity of the material. Now, the research is gearing up to design molecules with all three SCO, luminescence, and dielectric properties to provide magnetic optoelectronic materials that can be utilized for various molecular device applications and also there are several aspects which need