This study systematically investigated the durability of low-carbon concrete under severe service conditions using industrial solid wastes. The mechanical properties and carbonation resistance (including carbonation depth, compressive strength after carbonation, and splitting tensile strength after carbonation) were tested. Multi-scale characterization techniques, including XRD, SEM-EDS, and nanoindentation, were employed to investigate the microstructure. This approach revealed a synergistic mechanism linking microstructural evolution to the concrete’s macroscopic mechanical and durability performance. Results showed that incorporating 25% fly ash (FA) reduced compressive strength by 11.30% and 11.39% in CF-25 and BF-25 mixes, respectively, and increased carbonation depth by 58.46% in CF-25. In contrast, the addition of 5% silica fume (SF) produced different effects. It significantly enhanced the compressive strength of the CS-5 and BS-5 mixes by 18.92% and 9.94%, respectively. Furthermore, it improved the micromechanical properties of the interfacial transition zone (ITZ) and reduced its thickness. Micro-mechanistic analysis revealed that the low pozzolanic activity of FA at early ages led to insufficient hydration products, higher porosity, and a weaker ITZ. Conversely, SF, through its high pozzolanic reactivity and nano-filling effect, promoted a dense, highly polymerized gel structure and optimized pore size distribution. The distinct chemical characteristics of high-calcium and low-calcium cementitious systems further amplified the differential effects of these supplementary materials.