Electron–phonon coupling plays a key role in a variety of elemental excitations and their interactions in semiconductor nanostructures. Here we demonstrate that the relaxation rate of free excitons in a single ZnTe nanobelt (NB) is considerably enhanced via a nonthermalized hot-exciton emission process as a result of an ultrastrong electron–phonon coupling. Using time-resolved photoluminescence (PL) spectroscopy and resonant Raman spectroscopy (RRS), we present a comprehensive study on the identification and the dynamics of free/bound exciton recombination and the electron–phonon interactions in crystalline ZnTe NBs. Up to tenth-order longitudinal optical (LO) phonons are observed in Raman spectroscopy, indicating an ultrastrong electron–phonon coupling strength. Temperature-dependent PL and RRS spectra suggest that electron–phonon coupling is mainly contributed from Light hole (LH) free excitons. With the presence of hot-exciton emission, two time constants (80 and 18 ps) are found in photoluminescence decay curves, which are much faster than those in many typical semiconductor nanostructures. Finally we prove that under high excitation power amplified spontaneous emission (ASE) originating from the electron–hole plasma occurs, thereby opening another radiative decay channel with an ultrashort lifetime of few picoseconds.