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Limestone powder (LS) is a new environmentally-friendly concrete admixture, and its application in concrete engineering is worth exploring. The curing of LS hydraulic concrete under extreme temperatures will significantly affect the interior microstructure of concrete, which has a significant impact on the resistance to freeze-thaw cycles. This study aims to investigate the influence of LS replacement quantity (10 %, 30 % and 50 %) and curing temperatures (5 ℃, 20 ℃ and 50 ℃) on the freeze-thaw resistance of hydraulic concrete. The freeze-thaw resistance was reflected by the mass loss rate, relative dynamic modulus of elasticity (RDM) and ultrasonic inspection. The hydration products, microstructure and pore composition of LS hydraulic concrete were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) to dissect the underlying mechanisms behind the freeze-thaw resistance. The relationship between the pore composition and the mass loss rate and RDM was established to connect the microcosmic properties with the macroscopic properties. Findings from this study provide a guidance for the application of LS in concrete engineering under harsh environments.