Lanthanide (Ln3+)-doped phosphors generally suffer from thermal quenching, in which their photoluminescence (PL) intensities decrease at the higher temperature. Herein, we report a class of unique two-dimensional negative-thermal-expansion phosphor of Sc2(MoO4)3:Yb/Er. By virtue of the reduced distances between sensitizers and emitters as well as confined energy migration with increasing the temperature, a 45-fold enhancement of green upconversion (UC) luminescence and a 450-fold enhancement of near-infrared downshifting (DS) luminescence of Er3+ are achieved from 25 to 500 ˚C. The thermally boosted UC and DS luminescence mechanism is systematically investigated through in situ temperature-dependent Raman spectroscopy, synchrotron X-ray diffraction and PL dynamics. Moreover, the luminescence lifetime of 4I11/2 of Er3+ in Sc2(MoO4)3:Yb/Er displays a strong temperature dependence, enabling ratiometric thermometry with the highest relative sensitivity of 13.4%/K at 298 K. These findings may gain a vital insight into the design of negative-thermal-expansion Ln3+-doped phosphors for versatile applications.