The synthesis of reversible oligomer/polymers is fascinating both from the perspective of the fundamental understanding as well as their applications, ranging from biomedical to self‐healing smart materials. On the other hand, the reactions that occur in single‐crystal‐to‐single‐crystal (SCSC) fashion offer great details of the structure, geometry and stereochemistry of the product. However, SCSC 2+2 oligomerization is rather difficult and rare. Further, till date there are no reports for a reversible 2+2 oligomerization in SCSC fashion. In this work, four halogen‐substituted acrylic dienone molecules were deliberately designed and their ability to participate in 2+2 cycloaddition reaction in solid state was studied under visible light. Despite of having the required alignment of double bonds of dienes in all four crystal structures, they were found to exhibit variable reactivities given the differences in their weak intermolecular interactions such as halogen⋅⋅⋅halogen, halogen⋅⋅⋅π and C−H⋅⋅⋅O interactions. Notably, one of these materials exhibits reversible oligomerization in a SCSC manner. The first single‐crystal‐to‐single‐crystal reversible 2+2 photo‐oligomerization of conjugated dienones under visible light is reported.