Various push–pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition–retroelectrocyclization (CA–RE) reactions involving diverse electron-rich alkynes and electron-deficient alkenes. In this review, a comprehensive investigation of the recent and noteworthy advancements in the research on push–pull chromophores prepared via the [2 + 2] CA–RE reaction is conducted. In particular, an overview of the physicochemical properties of the family of these compounds that have been investigated is provided to clarify their potential for future applications.