White light emission with CIE-1931 coordinates close to the standard equal-energy white light illuminant, and color temperature in the 4000–6500K range was produced in Tm3+/Er3+-codoped glasses through frequency upconversion. Multi-Stokes Raman emissions generated in an optical fiber pumped at 1.064µm were used, seeking out the 3H5 thulium absorption band around 1.2µm as the departure point. The new and efficient excitation approach allowed the generation of near infrared (800nm), red (650nm), and blue (480nm) emission due to frequency upconversion excited via ground-state absorption and excited-state absorption in Tm3+ ions. Energy-transfer followed by excited-state absorption in Er3+ ions, provided the generation of the green (530, 550nm) and red (660nm) components to compose white light. The excitation mechanism for the Tm3+ ions is assigned to stepwise multi-wavelength excitation using Stokes Raman emission in an optical fiber, followed by stepwise excited-state absorption of the pump photons. Energy-transfer Tm3+[3F4] + Er3+[4I15/2] →Tm3+[3H6] + Er3+[4I9/2] followed by excited-state absorption of multi-Stokes Raman emissions populate erbium visible emitting level. Excitation power color tuneability of the overall light emission was also achieved.