Polymerization as a result of photocrosslinking is one of the most versatile technologies for producing organic polymers. This article highlights the formation of crosslinking in metal coordination polymers in the solid-state using a photochemical approach and its importance in material science. Past and current developments of solid-state photochemical [2+2] cycloaddition in organic and inorganic systems relevant to the topic are reviewed. The challenges for the coordination chemist in utilising this rational approach to orient the coordination polymers and the scope of this work are delineated.