Polyvinylpyrrolidone functionalized CaMoO4:Tb3+ were synthesized hydrothermally. The formation of tetragonal phase CaMoO4:Tb3+ and morphology of nanoparticles are thoroughly studied with XRD, TEM and FT-IR spectroscopy. Nanophosphors show green emission of Tb3+ at 544 nm when excited at 290 nm due to MoO42− absorption. The energy transfer from the host MoO42− to the activator Tb3+ is occurred mainly through dipole-dipole interactions. The decay lifetime of MoO42− emission decreases from ∼13 to 1 μs with the increase in Tb3+ concentration indicating occurrence of energy transfer. This is further corroborated with the calculation of radiative and non-radiative decay rates. The quantum yield and CIE color chromaticity are also studied.