In this study, it was demonstrated how second phases with small amount, which are hardly detected by XRD analysis, affect grain boundary dissolution and related mechanical properties of HA. All HA disks sintered at 1200 oC for 2 h in air with under moisture protection were phase pure and had Ca/P molar ratio of 1.67. Following certain period of exposure to the distilled water, the surface dissolution initiated at grain boundaries and particle loosening, subsequently resulting in decrease in mechanical properties of HA. In order to understand the dissolution mechanism, grain boundary structure of HA was identified by transmission electron microscopy (TEM) and high resolution TEM observation. From the analysis, it was found that the non-stoichiometric phase as α-tricalcium phosphate (TCP) transformed from β-TCP was existed at grain boundaries and caused surface dissolution of HA. From the XRD analysis, it was found that (211) and (112) planes of hydroxyapatite were susceptible to dissolution, whereas (300) plane was relatively stable.