AbstractThis work aims to improve the early age characteristics and water resistance of volcanic ash‐based phosphate geopolymer materials by modifying the chemistry of the binder with calcium hydroxide (CH). Phosphate geopolymer binders with Ca/P molar ratios ranging from 0.49 to 0.80 were prepared. Then the early and late age physical properties were then determined. The hardened binder was characterized by various analytical techniques involving XRD, TGA‐DSC, and SEM‐EDS. The results showed that the use of CH decreases the initial setting time from several hours to less than 5 min. At the same time, the 1 d compressive strength was increased from 0 to 15 MPa with the increase in the Ca/P molar ratio. Moreover, the slow dissolution rate of volcanic ash was responsible for the low strength at an early age but beneficial to improving the geopolymerisation with time. This favored the high strength of the control phosphate geopolymer, which reached 52.5 MPa at 56d and was higher than those with CH (28.5–45.2 MPa). However, the control phosphate geopolymer had poor water resistance, with strength retention ranging from 21%–57% compared to 76%–90% for phosphate geopolymer with CH. This is because of the leaching of the reactive phase underwater that inhibits further reaction progress. In addition, the modification of the binder chemistry with CH leads to the formation of new calcium phosphate phases that also contribute to enhancing water resistance.