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The gas‐liquid biphasic photochemical [2+2] cycloaddition of maleic anhydride with ethylene was identified as a desirable strategy for the divergent synthesis of cyclobutane derivatives. To address the challenge of utilizing this transformation on a larger scale, studies toward the development of a stable process with sufficient productivity were undertaken. These studies revealed the importance of several reaction parameters to enhance both the gas solubility in solution and the efficient utilization of photons from various types of light sources.