A high phosphorus Er3+/Yb3+ co-doped silica (EYPS) fiber core glass was prepared using the sol-gel method combined with high-temperature sintering. The absorption spectra, emission spectra, and fluorescence decay curves were measured and compared in temperatures ranging from 300 to 480 K. Compared to 915 and 97x nm, the absorption cross-section at ~940 nm (~0.173 pm2) demonstrates a weaker temperature dependence. Hence, the 940 nm pump mechanism is favorable for achieving a high-power laser output at 1.5 μm. Additionally, the double-exponential fluorescence decay of Yb3+ ions and the emission intensity ratio of I1018nm/I1534nm were measured to evaluate the energy transfer efficiency from Yb3+ ions to Er3+ ions. Through the external heating and active quantum defect heating methods, the emission intensity ratios of I1018nm/I1534nm increase by 30.6% and 709.1%, respectively, from ~300 to ~480 K. The results indicate that the temperature rises significantly reduce the efficiency of the energy transfer from the Yb3+ to the Er3+ ions.