Cyanines are emerging as useful agents for photoreleasing biological compounds because of their capability of utilizing near‐infrared (NIR) light. Another benefit is their ability to self‐sensitize to produce singlet oxygen for the release of aryl amines, a process that has not been as feasible in the past. Here, we highlight the paper by Schnermann et al. (https://doi.org/10.1111/php.13090), which reports on a cyanine conjugate for heterolytic photocleavage of aryl amines. This paper is timely—delving into a photorelease mechanism involving a domino rearrangement and β‐elimination triggered by NIR light.