Cr(3+)-activated mullite-type Bi2Ga(4-x)Al(x)O9 (x = 0, 1, 2, 3, and 4) solid solutions were prepared by the solid state reaction, and their spectroscopic properties were investigated in conjunction with the structural evolution. Under excitation at 610 nm, Bi2[Ga(4-y)Al(y)]3.97O9:0.03Cr(3+) (y = 0, 1, 2, 3, and 4) phosphors exhibited broad-band near-infrared (NIR) emission peaking at ∼710 nm in the range 650-850 nm, and the optimum Cr(3+) concentrations and concentration quenching mechanism were determined. Except for the interesting NIR emission, the body color changed from white (at x = 0) to green (at x = 0.08) for Bi2Ga(4-x)O9:xCr(3+), and from light yellow (at x = 0) to deep brown (at x = 0.08) for Bi2Al(4-x)O9:xCr(3+), respectively. Moreover, as a result of variable Al/Ga ratio, the observed body color for Bi2[Ga(4-y)Al(y)]3.97O9:0.03Cr(3+) (y = 0, 1, 2, 3, and 4) varied from deep brown to green. The relationship between the observed colors and their diffuse reflectance spectra were also studied for the understanding of the different absorption bands. The results indicated that Cr(3+)-doped Bi2Ga(4-x)Al(x)O9 solid solutions appeared as the bifunctional materials with NIR phosphors and color-tunable pigments.