The electronic structure of four ternary-metal oxides containing isolated vanadate ions is studied. Zircon-type YVO4, YbVO4, LuVO4, and NdVO4 are investigated by high-pressure optical-absorption measurements up to 20 GPa. First-principles calculations based on density-functional theory were also performed to analyze the electronic band structure as a function of pressure. The electronic structure near the Fermi level originates largely from molecular orbitals of the vanadate ion, but cation substitution influences these electronic states. The studied orthovanadates, with the exception of NdVO4, undergo a zircon-scheelite structural phase transition that causes a collapse of the band-gap energy. The pressure coefficient dE(g)/dP shows positive values for the zircon phase and negative values for the scheelite phase. NdVO4 undergoes a zircon-monazite-scheelite structural sequence with two associated band-gap collapses. (C) 2011 American Institute of Physics. [doi:10.1063/1.3626060]