In this research, nanoscale Ca-α-SiAlON:Eu2+ phosphor is formed by pulsed laser ablation (1.27 J/pulse cm2) in deionized water. Analyses of particle size and composition are accomplished by transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. High-resolution TEM (HR-TEM) shows that the nanoparticles are highly crystalline and EDS confirms their composition. The emission spectrum of the nanoscale Ca-α-SiAlON:Eu2+ shows an obvious blue shift compared with that shown by the target, possibly resulting from changes in the crystal field around Eu2+ caused by the enhancement of surface effects due to the nanoscale size.