Preparation of Li1−mAgmLa0.99−nYnPr0.01(MoO4)2 phosphors was done by a convenient method of solid-state reaction technique in the air. The effects of synthesis temperature, substitution of Ag+, Y3+ on the LiLa(MoO4)2 crystal structure, and luminescence properties of Pr3+ in the molybdate host are investigated systematically. The observed excitation and emission spectra indicate that the phosphor can be excited effectively by the blue light (440–500 nm) and exhibit a satisfactory red emission at 605 and 649 nm, respectively. The substitution of a little Ag+ for Li+ enhances the Pr3+ luminescence intensity drastically. The variability of Y3+ and La3+ content changes the emission intensity ratio of the 1D2 → 3H4 and 3P0 → 3F2 transition, so that the CIE chromaticity coordinates of the as-prepared Li1−mAgmLa0.99−nYnPr0.01(MoO4)2 phosphors are tuned from (0.639, 0.351) to (0.653, 0.337).