The effect of curing regime on degree of Al3+ substituting for Si4+(Al/Si ratio) in C-S-H gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning(MAS) nuclear magnetic resonance(NMR) with deconvolution technique. The curing regimes included the constant temperature(20, 40, 60 and 80 ℃) and variable temperature(simulated internal temperature of mass concrete with 60 ℃ peak). The results indicate that constant temperature of 20 ℃ is benefi cial to substitution of Al3+ for Si4+, and Al/Si ratio changes to be steady after 180 d. The increase of Al/Si ratio at 40 ℃ is less than that at 20 ℃ for 28 d. The other three regimes of high temperature increase Al/Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ℃ curing stage from 28 to 180 d at variable temperature regime, is benefi cial to the increase of Al/Si ratio which is still lower than that at constant temperature regime of 20 ℃ for the same age. A nonlinear relation exists between the Al/Si ratio and temperature variation or mean chain length(MCL) of C-S-H gels, furthermore, the amount of Al3+ which can occupy the bridging tetrahedra sites in C-S-H structure is insuffi cient in hardened Portland cement pastes. The effect of curing regime on degree of Al3 + substituting for Si4 + (Al / Si ratio) in CSH gels of hardened Portland cement pastes was investigated by 29Si magic angel spinning (MAS) nuclear magnetic resonance (NMR) with deconvolution technique. The curing regimes included the constant temperature (20, 40, 60 and 80 ° C) and variable temperature (simulated internal temperature of mass concrete with 60 ° C peak). The results indicate that constant temperature of 20 ° C is beneficially substituted for Al3 + for Si4 +, and Al / Si ratio changes to be steady after 180 d. The increase of Al / Si ratio at 40 ° C is less than that at 20 ° C for 28 d. The other three regimes of high temperature increase Al / Si ratio only before 3 d, on the contrary to that from 3 to 28 d. However, the 20 ° C curing stage from 28 to 180 d at variable temperature regime, is benefi cial to the increase of Al / Si ratio which is still lower than that at constant temperature regime of 20 ° C for the same age. A nonlinear relat ion exists between the Al / Si ratio and temperature variation or mean chain length (MCL) of C-S-H gels, furthermore, the amount of Al3 + which can occupy the bridging tetrahedra sites in C-S-H structure is insuffient in hardened Portland cement pastes.