AbstractRNA‐based tools for biological and pharmacological research are raising an increasing interest. Among these, RNA aptamers whose biological activity can be controlled via illumination with specific wavelengths represent an important target. Here, we report on a proof‐of‐principle study supporting the viability of a systematic use of Morita‐Baylis‐Hillman adducts (MBHAs) for the synthesis of light‐responsive RNA building blocks. Accordingly, a specific acetylated MBHA derivative was employed in the functionalization of the four natural RNA bases as well as two unnatural bases (5‐aminomethyl uracil and 5‐methylaminomethyl uracil). The results reveal a highly selective functionalization for both unnatural bases. The conjugation products were then investigated spectroscopically, photochemically and computationally. It is shown that when a single light‐responsive unit is present (i. e. when using 5‐methylaminomethyl uracil), the generated unnatural uracil behaves like a cinnamic‐framework‐based photochemical switch that isomerizes upon illumination through a biomimetic light‐induced intramolecular charge transfer mechanism driving a barrierless and, therefore, ultrafast reaction path.