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Environmental condition affects the property of construction materials. This study gives an initial understanding of Portland cement hydration under low temperatures from the views of laboratory experiments (including electrical resistivity, degree of hydration (DoH), and maturity) as well as thermodynamic calculation. The hydrates of Portland cement at the given period were detected with X-ray diffraction (XRD), and their microstructure was observed by scanning electron microscope (SEM). Experiment result (i.e., DoH and electrical resistivity) indicated that the hydration of Portland cement was delayed by low temperature without hydration stopping at −5 ∘ C. Based on a basic kinetics model, the thermodynamic calculation predicted that the final hydrate differs in dependence on environmental temperatures. The mechanical behavior trend of Portland cement paste affected by low temperatures potentially is linked to the appearing of aluminate compounds and reduction of portlandite.