Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO4)2 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO4)2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.