This research addresses a notable gap in understanding the synergistic effects of high carbon wood bottom ash (BA) and silica fly ash (FA) on cement hydration and concrete durability by using them as a supplementary material to reduce the amount of cement in concrete and CO2 emissions during cement production. This study analyses the synergistic effect of FA and BA on cement hydration through X-ray diffraction (XRD), thermal analysis (TG, DTG), scanning electron microscopy (SEM), density, ultrasonic pulse velocity (UPV), compressive strength, and temperature monitoring tests. In addition, it evaluates concrete properties, including compressive strength, UPV, density, water absorption kinetics, porosity parameters, predicted resistance to freezing and thawing cycles, and results of freeze–thawing resistance. The concrete raw materials were supplemented with varying percentages of BA and FA, replacing both cement and fine aggregate at levels of 0%, 2.5%, 5%, 10% and 15%. The results indicate that a 15% substitution of BA and FA delays cement hydration by approximately 5 h and results in only a 6% reduction in compressive strength, with the hardened cement paste showing a strength similar to a 15% replacement with FA. Concrete mixtures with 2.5% BA and 2.5% FA maintained the same maximum hydration temperature and duration as the reference mix. Furthermore, the combined use of both ashes provided adequate resistance to freeze–thaw cycles, with only a 4.7% reduction in compressive strength after 150 cycles. Other properties, such as density, UPV and water absorption, exhibited minimal changes with partial cement replacement by both ashes. This study highlights the potential benefits of using BA and FA together, offering a sustainable alternative that maintains concrete performance while using waste materials.