AbstractPhoton avalanche (PA) is a highly nonlinear mode of upconversion that is characterized by 100–1000‐fold increase in luminescence intensity upon minute increments of pumping power. The practical realization of numerous possible nano‐bio‐technology applications utilizing the PA phenomenon will require information on its susceptibility to the material volume and surface. Here, these parameters are investigated via experimental and theoretical PA. The two‐color, highly nonlinear PA emission at 475 and 800 nm is clearly observed in bulk single crystal, individual microcrystals, and ensembles of colloidal core and core–shell nanoparticles of LiYF4 host doped with either 3 or 8% of thulium ions. The properties of PA emission, such as PA nonlinearity, PA gain, PA intensity, and luminescence kinetics in these materials show dependence on crystal volume and surface quenching. Theoretical simulations provide understanding of key physical processes that influence PA performance. Moreover, photon avalanche single beam super‐resolution imaging is realized for the first time in 3% Tm3+ doped LiYF4 core–shell nanoparticles. The obtained insights and predictions form a solid background for further development and applications of new optimized PA materials.