Triplet‐triplet annihilation upconversion (TTA‐UC) has made significant progress in recent years in several key applications, including solar energy harvesting, photocatalysis, stereoscopic 3D printing, and disease therapeutics. In TTA‐UC research, photosensitizers serve the vital function of harvesting low‐energy photons. The photophysical characteristics of photosensitizers, including absorbance, triplet state quantum yield, triplet state energy level, triplet state lifetime, etc., determine the performance of TTA‐UC. Thus, the study of photosensitizers has been a key aspect of TTA‐UC. In recent years, multi‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have received extensive attention due to their excellent photophysical properties and electroluminescent device performance. MR‐TADF molecules not only present a narrow energy gap between the singlet and triplet excited states, but also have stronger absorption and better wavelength regulation than conventional TADF molecules. Nowadays, the preliminary attempts in TTA‐UC using MR‐TADF molecules as photosensitizers have resulted in the development of green to ultraviolet, blue to ultraviolet, and even near‐infrared to blue emission. This concept will summarize the research progress of MR‐TADF molecules as photosensitizers in TTA‐UC, analyzing the challenges and giving possible solutions. Finally, we prospect the future development of MR‐TADF molecules as photosensitizers, including the molecular design as well as the possible application areas.