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Controlling the photoreactivity of the solids, especially metal complexes, coordination polymers (CPs) and metal-organic frameworks (MOFs) is a challenging task in the past. But now it is possible to design a reactive solid using the crystal engineering principles with ease than ever before. For the past several years, our research group is actively involved in designing photoreactive solids that can undergo structural transformation by [2+2] cycloaddition reactions under UV light in the solid state. In this talk some of the recent developments in this area from our laboratory will be presented. This includes polymerization of metal complexes, polymerization of organic ligands inside MOFs via [2+2] cycloaddition reactions forming MOF-COF hybrid structures, photosalient behavior of metal complexes during photodimerization process under UV light (shown in Figure 1), reversible formation and cleavage of cyclobutane rings in MOFs, unusual [2+2] cycloaddition reactions between phenyl and olefin bonds and unusual structural transformation during this process.