This study investigated the nature of hydration products of white portland cement(WPC) containing 20 m M malic acid or 1 M calcium chloride hydrated for 11 years. The study identified the hydration products and characterized the chemical composition, morphology, micro/nano structure of C-S-H and the main binding phase in cementitious materials. Calcium hydroxide(CH), ettringite and C-S-H were identified in WPC with 20 m M malic acid paste hydrated for 11 years. WPC with 1 M calcium chloride paste hydrated for 11 years contained the same phases, but with less CH, and the presence of Friedel’s salt(Ca2Al(OH)6Cl·2H2O). There were still small amount of anhydrous cement particles remaining in both pastes after 11 years hydration according to the SEM and 29 Si MAS NMR results. The hydration products of paste containing malic acid had a lower porosity than those prepared with calcium chloride upon visual inspection under SEM. The morphology of the outer product(Op) C-S-H was coarse fibrillar and the inner product(Ip) C-S-H had a very fine microstructure in both pastes under TEM. Both Ip and OpC-S-H formed in paste containing malic acid had lower Ca/Si and higher Al/Si than those in paste containing calcium chloride. C-S-H in paste containing calcium chloride had longer MCL and less percentage of bridging tetrahedra occupied by aluminum in silicon/aluminum chains due to relatively less Q1 and more Q2. A new type of silicon tetrahedra, Q2B, was introduced during deconvolution of 29 Si MAS NMR results. Ip and Op C-S-H in both pastes had aluminum substituted tobermorite-type and jennite-type structure, and all the charges caused by aluminum substituting silicon bridging tetrahedra were balanced by Ca2+. This study investigated the nature of hydration products of white portland cement (WPC) containing 20 m M malic acid or 1 M calcium chloride hydrated for 11 years. The study identified the hydration products and characterized the chemical composition, morphology, micro / nano structure of Calcium hydroxide (CH), ettringite and CSH were identified in WPC with 20 m M malic acid paste hydrated for 11 years. WPC with 1 M calcium chloride paste hydrated for 11 years contained the same phases , but with less CH, and the presence of Friedel’s salt (Ca2Al (OH) 6Cl · 2H2O). There were still small amount of anhydrous cement particles remaining in both pastes after 11 years hydration according to the SEM and 29 Si MAS NMR results. The hydration products of paste containing malic acid had a lower porosity than those prepared with calcium chloride upon visual inspection under SEM. The morphology of the outer product (Op) CSH was coarse fibrillar Both Ip and OpC-SH formed in paste containing malic acid had lower Ca / Si and higher Al / Si than those in paste containing calcium chloride. CSH had a very fine microstructure in both pastes under TEM. in paste containing calcium chloride had longer MCL and less percentage of bridging tetrahedra occupied by aluminum in silicon / aluminum chains due to less Q1 and more Q2. A new type of silicon tetrahedra, Q2B, was introduced during deconvolution of 29 Si MAS NMR results . Ip and Op CSH in both pastes had aluminum substituted tobermorite-type and jennite-type structure, and all the charges caused by aluminum substituting silicon bridging tetrahedra were balanced by Ca2 +.