White-light-emitting devices (WLEDs) are considered to be a promising illumination source; especially, the WLEDs based on carbon dots (CDs) with white fluorescence have attracted extensive research interest. Herein, we report the design and implementation of solid white-light-emitting phosphors (WCDs@PS), which combine blue and orange emissive CDs (BCDs and OCDs) assisted by polystyrene (PS) through a self-assembly technique. Based on these phosphors (OCDs/BCDs = 1.2:1), the obtained WLEDs display a warm white light with International Commission on Illumination (CIE) coordinates of (0.35, 0.36), a high color rendering index of 93.2, a low correlated color temperature of 4075 K, and a luminous efficiency of up to 14.8 lm·W–1. Interestingly, these WLEDs exhibit temperature-dependent emission performance, whose light-emission spectrum can be adjusted in situ from white (λ ∼ 400–730 nm) to blue (λ ∼ 440 nm) in the range of 20–80 °C. A change in CIE coordinates from (0.35, 0.36) to (0.32, 0.23) was also observed. The temperature-driven tunable LEDs as a thermochromism device could broaden the application of CDs-based lighting systems in special displays.