Concrete in saline or coastal settings exposed to freezing temperatures is frequently affected by coupling actions of sulfate assault and freeze–thaw degradation, reducing the service life of concrete structures significantly. This study conducted an accelerated freeze–thaw cycle test in pure water and Na2SO4 solution with a mass proportion of 5% to examine the coupling impact of sulfate freeze–thaw on the frost resistance of composite limestone powder (CLP) concrete. Combined with SEM and XRD methods, the performance degradation mechanisms of composite limestone powder (CLP) concrete in coupling sulfate freeze–thaw conditions were analyzed with a microscopic point of view. The findings demonstrated that limestone powder has a filling effect but the activity is low. When the content is 10~20%, the chemical response is higher than the physical response. The pozzolanic effect of fly ash and slag can improve the pore structure and improve the compactness of concrete. The “superposition effect” of limestone powder, fly ash, and slag can improve the frost resistance of CLP concrete. The scenario of salt freezing cycles has negative effects that are worse than those of water freezing cycles on the antifreeze performance of CLP concrete, including apparent morphology, mass loss, relative dynamic modulus of elasticity, and compressive strength. Sulfate’s activation effect boosts slag’s activity effect, which significantly promotes the antifreeze performance of concrete subjected to salt frozen cycles over water frozen cycles. The freeze–thaw damage model of CLP concrete under coupling sulfate freeze–thaw is established through theorem analysis and experiment statistics, laying a theoretical framework for the popularization and use of this concrete.