Novel near infrared (NIR) emitting phosphor, CaYAl3O7:Ce3+,Nd3+,Yb3+ was synthesized by one step combustion synthesis and characterized with X-ray diffraction, photoluminescence emission, photoluminescence excitation spectra and fluorescence decay measurements. Intense NIR emissions which are assigned to the characteristic 4I9/2,11/2,13/2 transitions of Nd3+ along with broadband emission of Ce3+ at 420 nm was observed under 360 nm excitation. The fluorescence decay measurements and energy transfer efficiency of Ce3+ in CaYAl3O7 doped with Ce3+-Nd3+ and Ce3+-Nd3+-Yb3+ are also compared. The influence of Yb3+ doping concentration on the emission of Ce3+, Nd3+ and Yb3+ in CaYAl3O7 is studied. Two step sensitization of Yb3+ through efficient energy transfer Ce3+→Nd3+→Yb3+ is also investigated with the aim of achieving NIR emission of Yb3+. The results indicate that sensitization of Yb3+ is possible through Ce3+ via Nd3+ intermediate.