Yb3+/Tm3+: CaYAlO4 (CYA) and Nd3+/Yb3+/Tm3+: CYA bulk single crystals were grown using the Czochralski (Cz) method. The polarized absorption, upconversion luminescence (UCL) spectra under 980 nm and 808 nm pumping, and fluorescence decay curves were measured as well as Judd-Ofelt (J-O) theory calculations were performed to investigate the sensitization effect of Yb3+ and Nd3+/Yb3+co-doping in Tm3+: CYA single crystal. Obvious enhancement was observed in Tm3+-activated crystals for the blue upconversion emission (∼474 nm) when doped with Yb3+ or co-doped with Nd3+/Yb3+. The energy transfer efficiency is 72.6% (Yb3+→Tm3+) and 71.7% (Nd3+→Yb3+/Tm3+) in Yb3+/Tm3+: CYA and Nd3+/Yb3+/Tm3+: CYA single crystals respectively. The gain cross-sections were calculated, and it can stated that the blue laser output derived from upconversion is possible around 474 nm related to the transition of 1G4→ 3H6 in Yb3+/Tm3+: CYA and Nd3+/Yb3+/Tm3+: CYA crystals.