The exploration relevant to the surface changes on optical micro- and nanofibers (MNFs) is still in infancy, and the reported original mechanisms remain long-standing puzzles. Here, by recognizing the combined interactions between fiber heating, mechanically tapering, and high-power pulsed laser guiding processes in MNFs, we establish a general thermal-mechanical-photo-activation mechanism that can explain the surface changes on MNFs. Our proposed activation mechanism can be well supported by the systematical experimental results using high-intensity nanosecond/femtosecond pulsed lasers. Especially we find large bump-like nanoscale cavities on the fracture ends of thin MNFs. Theoretically, on the basis of greatly increased bond energy activated by the fiber heating and mechanically tapering processes, the energy needed to break the silicon-oxygen bond into dangling bonds is significantly reduced from its intrinsic bandgap of ∼9 eV to as low as ∼4.0 eV, thus high-power pulsed lasers with much smaller photon energy can induce obvious surface changes on MNFs via multi-photon absorption. Finally, we demonstrate that using surfactants can repair the MNF surfaces and exploit them in promising applications ranging from sensing and optoelectronics to nonlinear optics. Our results pave the way for future preventing the performances from degradation and enabling the practical MNF-based device applications.