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Early freezing of concrete is common in the construction of water conservancy projects in northern China. Early freezing damage induces the deterioration of the mechanical properties of concrete structures, which seriously affects the safety, stability, and service life of engineering structures. Through a laboratory uniaxial compression test and a computed tomography (CT) test, the influence law of freezing time and freezing temperature on the mechanical properties of concrete is analyzed herein. The three-dimensional pore structure of concrete at different freezing times is reconstructed. The pore distribution and pore structure characteristic parameters of concrete at different freezing times are studied. The correlation between mechanical properties and the pore structure of early frozen concrete is determined. The results show that with the delay of freezing time, the porosity of concrete test blocks increases first and then decreases. The average pore surface area primarily decreases and then increases. The average pore diameter increases with the trend of a quadratic parabola. The average pore form factor primarily decreases, then increases, and then decreases. The average pore surface area has the best correlation with the compressive strength and elastic modulus of early frozen concrete. The outcomes suggest that the average pore surface area should be preferred when constructing the mesoscopic damage index of early frozen concrete. Relevant results provide support for revealing the macro and micro damage mechanisms of early frozen concrete.