A new method involving the extraction of various ions from hardened cement pastes by anhydrous ethanol is presented to determine the pH value and ionic concentration during the first 28 days. The volume content of pore solution extracted by ethanol in the leachate reached 12% or above and the pH values calculated by alkali ions are more than 12, even up to 12.73. The results were compared with those from parallel, conventional pore water expression experiments. All of these comparisons verified the feasibility of the proposed method. However, the application of this method to pore solution analysis needs further improvement.