Nonradiative decay invariably competes with radiative decay during the deexcitation process of matter. In the community of luminescence research, nonradiative decay has been deemed less attractive than radiative decay. However, all things in their being are good for something and so is nonradiative decay. As the molecular motion‐facilitated nonradiative decay (MMFND) effect is inevitable in photophysical processes, it provides a new avenue to convert the harvested light energy into exploitable forms by harnessing molecular motion. In many cases, active molecular motion enables thermal deactivation from excited states. In this Minireview, recent advances in photothermal and photoacoustic systems with MMFND character are summarized. We believe that this presentation of the rational engineering of molecular motion for efficient photothermal generation will deepen the understanding of the relationship between molecular motion and nonradiative decay and navigate people to rethink the positive aspects of nonradiative decay for the establishment of new light‐controllable techniques. In the past few years, the molecular motion‐facilitated nonradiative decay (MMFND) effect has been widely used to develop efficient photothermal and photoacoustic systems. To give a timely summary of this emerging field, the present Minireview systematically highlights the underlying mechanism, molecular design principles, and advanced applications of photothermal transduction agents with flexible molecular groups.