Due to the widely tunable band gap and broadband excitation, CdS quantum dots (QDs) show great promise for yellow-light luminescence center in white-light-emitting devices. The light intensity of the CdS QD-doped glass was enhanced by doping the Tm3+ ions due to the higher absorption rate. The influence of Tm3+ ions on the surface structure of CdS QDs was enormous according to the first-principles calculations. Doping Tm3+ ions change the surface state of CdS QDs, which will fix the QDs emission peaks and enhance the luminescence of CdS QDs at a lower heat-treatment temperature. White-light emission was obtained by tuning the relative concentration between Tm3+/CdS QDs. However, there is a fundamental challenge to fabricate QD-doped glass fibers by rod-in-tube method since uncontrollable QDs crystallization is hard to avoid. Herein, a white-light-emitting borosilicate glass fiber was fabricated by the "melt-in-tube" method using a special designed Tm3+/CdS QDs co-doped borosilicate glass with low-melting temperature as fiber core. After heat treatment, ideal white-light emission was observed from the fiber under excitation at single wavelength (359 nm). This finding indicates that Tm3+/CdS QDs co-doped glass fiber with white-light-emitting devices has potential application as gain medium of white-light-emitting sources and fiber lasers.