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Molecular crystals with the ability to transform light energy into macroscopic mechanical motions are a promising class of materials with potential applications in actuating and photonic devices. In regard to such materials, coordination polymers that exhibit dynamic photomechanical motion, associated with a phase transition, are unknown. Herein, we report an intriguing photoactive, one‐dimensional ZnII coordination polymer, 1, derived from 1,3,5‐tri‐4‐pyridyl‐1,2‐ethenylbenzene and 3,5‐difluorobenzoate. Single crystals of 1 under UV light irradiation exhibit rapid shrinking and bending, violent bursting‐jumping, splitting, and cracking behavior. Single‐crystal X‐ray diffraction analysis and 1H NMR spectroscopy reveal an unusual photoinduced phase transition involving a single‐crystal‐to‐single‐crystal [2+2] cycloaddition reaction that results in photomechanical responses. Interestingly, crystals of 1, which are triclinic with space group P1‾ ${P\bar{1}}$ , are transformed into a higher symmetry, monoclinic cell with space group C2/c. This process represents a rare example of symmetry enhancement upon photoirradiation. The photomechanical activity is likely due to the sudden release of stress associated with strained molecular geometries and significant solid‐state molecular movement arising from cleavage and formation of chemical bonds. A composite membrane fabricated from 1 and polyvinyl alcohol (PVA) also displays interesting photomechanical behavior under UV light illumination, indicating the material's potential as a photoactuator. [ABSTRACT FROM AUTHOR]