The synthesis conditions of the Yb3+ and Tb3+ co-doped NaYF4 were optimized by reducing the number of washings to include only ethanol. The avoidance of the loss of amorphous NaF prior to post-annealing of the as-prepared materials resulted in the enhancement of the otherwise rather weak up-conversion from Tb3+ by 1–2 orders of magnitude. At the same time, the temperature of formation of the hexagonal NaRF4 phase with high up-conversion could be lowered by 100°C down to 350°C. This improvement in up-conversion was concluded to result from the better stoichiometry of the material without washing with water. The deficit of Na+ would result in the excess of fluoride which, although not as fatal to the luminescence as the fluoride vacancies, has serious implications to the up-conversion intensity. A further enhancement in the up-conversion luminescence was observed to be due to the Er3+ ion impurity frequently associated with high-concentration Yb3+ materials. The mechanism involving the unintentional Er3+ sensitizer and the resonance energy transfer in the Yb3+–Er3+–Tb3+ co-doped NaYF4 were discussed based on the energy level schemes of the Yb3+, Er3+, and Tb3+ ions in NaYF4.