Coordination polymers (CPs) have attracted significant attention due to their structural diversity and tunable properties, enabling applications in energy storage, molecular storage, and drug delivery. Their structures and functions can be effectively controlled through ligand design, solvent environment, and post-synthetic modification. In this study, five coordination polymers were synthesized and structurally characterized through direct synthesis and post-synthetic transformation. CPs 2 and 4, obtained from different solvent systems, incorporate solvent molecules as guests within their frameworks. Olefin-containing linkers enable solid-state [2+2] photocycloaddition to form cyclobutane units, producing CPs 3 and 5 upon UV irradiation. These results show that structural diversity and photoreactivity depend strongly on linker identity and solvent environment, highlighting their potential as tunable functional solid-state materials.