In recent years, mechanoluminescence from polymers is emerging as a new cutting-edge area of polymer mechanochemistry research. It refers to the release of energy from polymers in the form of light when they are under various mechanical stimuli. To spur more researchers to join in such interesting and new burgeoning area, and promote its development to practical applications, in this review, we try to briefly summarize the recent advances in mechanoluminescent polymers with the aspects of non-covalent, covalent, and cascade reactions systems. We pay much attention on the applications of such polymer systems in molecular level failure and stress sensors, and give a perspective of their potential applications in novel energy conversion materials and devices, as well as self-healing materials.