Yb3+/Er3+/Tm3+ and Yb3+/Er3+/Tm3+/Ho3+ doped α-NiMoO4 nanoparticleswere synthesized by microwave hydrothermal method and studied for white light emission under 980 nm laser diode excitation. White upconversion (UC) light was successfully obtained with the appropriate control of blue, green, and red emissions via successfully tuning Er3+ and Ho3+ concentration in Yb3+/Er3+/Tm3+ and Yb3+/Er3+/Tm3+/Ho3+ doped α-NiMoO4, respectively. In addition, the white color emission was also shown by the CIE chromaticity coordinates of samples. The energy transfer mechanisms were explained in detail based on emission spectra and pump power density-dependent UC luminescence intensity in rare earth (Yb3+/Er3+/Tm3+ and Yb3+/Er3+/Tm3+/Ho3+) doped α-NiMoO4 nanoparticles. The results indicate thatYb3+/Er3+/Tm3+ and Yb3+/Er3+/Tm3+/Ho3+ doped α-NiMoO4 nanoparticles can be good candidates for white light device.