In this work, we explore detailed energy transfer processes between Nd3+ and Yb3+ ions in silicate glasses. The absorption, temperature dependent emission spectra and decays of Yb3+ and Nd3+ singly doped and Nd3+/Yb3+ co-doped silicate glasses were measured and analyzed. The phonon assisted Nd3+→Yb3+ energy transfer was investigated. The phonons of 621 cm−1 and 1090 cm−1 contributing greatly to accelerate the energy transfer Nd3+ → Yb3+ and Yb3+ → Nd3+, respectively. The energy transfer efficiencies between Yb3+ and Nd3+ ions were theoretically and experimentally studied. We find that the cumulative time decreased with increasing temperature for Nd3+→Yb3+, whereas the cumulative time peaked at 350 K for Yb3+→Nd3+. We report increased energy transfer efficiencies of Nd3+→Yb3+ (73.19–82.31%) and Yb3+→Nd3+ (9.97–18.11%) with increasing temperature implying Nd3+ and Yb3+ co-doped silicate glass may be a promising candidate for efficient temperature sensors.