Optical tuning of lanthanide-doped upconversion nanoparticles has attracted considerable attention over the past decade because this development allows the advance of new frontiers in energy conversion, materials science, and biological imaging. Here we present a rational approach to manipulating the spectral profile and lifetime of lanthanide emission in upconversion nanoparticles by tailoring their nonlinear optical properties. We demonstrate that the incorporation of energy distributors, such as surface defects or an extra amount of dopants, into a rare-earth-based host lattice alters the decay behavior of excited sensitizers, thus markedly improving the emitters' sensitivity to excitation power. This work provides insight into mechanistic understanding of upconversion phenomena in nanoparticles and also enables exciting new opportunities of using these nanomaterials for photonic applications.