A series of emission-tunable Na1-xAl1+2xSi1-2xO4:xBi(3+)/Eu3+ phosphors were synthesized via high temperature solid-state reaction method. The luminescence properties, energy transfer from Bi3+ to Eu3+ ions, color tuning, thermal stability and quantum efficiency were systematically investigated. Especially, in the host, a certain amount of Si4+ were replaced by Al3+ in order to remedy the charge compensating defect, so that, the emission intensity had been improved. The results of Rietveld refinements, the analysis of SEM mapping and the fourier transform infrared (FT-IR) indicated that this charge balance strategy was an effective method. Meanwhile, the energy transfer from Bi3+ to Eu3+ can be inferred and confirmed and the mechanisms were demonstrated to quadrupole-quadrupole interaction. The emission hue can be tuned from blue to pink, and finally to orange red light by properly varying the ratio of Bi3+ and Eu3+. Importantly, when the temperature was raised to 150 degrees C, the integrated emission intensity was 71.20% of the initial value for NAS:1%Bi3+,2%Eu3+ samples indicating that these phosphors had excellent thermal stability and stable color (no emission shift). All these properties indicate that the developed phosphors may be potentially used as single-component color-tunable-emitting phosphors for UV light-emitting diodes.