This paper describes the investigation into the use of cathodoluminescence for distinguishing HA and β-TCP phases within the biphasic calcium phosphate ceramic microstructure. Polished samples were scanned using SEM-CL at an accelerating voltage in the range of 10-15 keV with a beam current of 5-10 nA. The grayscale images produced reveal distinctive patterns for each composition. EDS and EPMA suggest chemical differences among the contrasting regions. Image analysis of voxel values indicate that areas of bright contrast correspond to β-TCP grains with phase amounts confirmed by XRD.