A three key parameters (SiO/AlO, MO/AlO and HO/MO, M denotes Na or K) composition design method was firstly proposed based on chemical characteristics analysis of calcined kaolin-based geopolymer cement. A total of 9 Na-poly-sialate-disiloxo (Na-PSDS) geopolymer cement pastes with different mole ratio of SiO/AlO, NaO/AlO, HO/NaO were designated to investigate the influence of the three key ratios on mechanical properties and microstructure in accordance with orthogonal design. The results showed that the ratios NaO/AlO and HO/NaO had significant effect on compressive strength. The highest compressive strength (34.9 MPa) was achieved at SiO/AlO = 5.5, NaO/AlO = 1.0 and HO/NaO = 7.0. Comparing the IR spectra of the 9 pastes also indicated that cement with the highest strength was the most fully reacted one and possessed the largest amount of geopolymers. The microscopic analysis revealed that the fully reacted Na-PSDS cement possessed structural characteristics similar to gel substances in having a wide range of Si endowments, but the framework of SiO tetrahedra partially replaced by 4-coordinated Al. © 2009 Elsevier B.V. All rights reserved.