The main concern of this work is to evaluate the influences of supplementary cementitious materials (fly ash, slag) and a new type of polycarboxylate superplasticizer containing viscosity modifying agents (PCE-VMA) on the performance of self-compacting concrete (SCC). The workability, hydration process, mechanical property, chloride permeability, degree of hydration and pore structure of SCC were investigated. Results indicate that the addition of fly ash and slag slows down early hydration and decreases the hydration degree of SCC, and thus leads to a decline in compressive strengths, especially within the first 7 days. The addition of slag refines pore structure and contributes to lower porosity, and thus the chloride permeability of SCC is decreased during the late hydration stage. Additionally, a new factor of calculated water–binder ratio is put forward, which can directly reflect the free water content of concrete mixture after mixing, and guide the mix proportion design of SCC.