To achieve sustainable utilization of a large amount of mine solid waste, this study investigated the performance of self-compacting coal gangue-filled backfill (SCFB) containing biomass fly ash (BFA) generated from biomass power plants as a supplementary cementitious material (SCM). The correlations between the physical structure and compressive strength of SCFB samples were obtained by ultrasonic pulse velocity (UPV). The failure process of the SCFB samples was monitored by the digital image correlation (DIC) technique, and the stress–strain relationship and failure pattern were also analyzed. The micro-morphological structure and hydration products of SCFB samples were evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and backscattered electron imaging (SEM-BSE). The results show that the usage of 30~40% BFA in SCFB improves the physical structure and strength of the samples. The compressive strength and UPV value of SCFB samples with different water-to-cement (w/c) ratios showed a similar trend of increasing and then gradually decreasing as the proportion of ordinary Portland cement (OPC) replaced by BFA increased. BFA exhibits better reactivity and filling effect in SCFB samples with a high w/c ratio. The peak stress of SCFB samples gradually decreases, and resistance to deformation gradually weakens with the increase in w/c ratios, while the DIC results further verify the mechanical experimental results. Microstructural analysis revealed that reducing the w/c ratio and incorporating specific ratios of BFA can reduce the thickness of the interface transition zone (ITZ) and porosity. The results of the study will provide theoretical guidance for the modification, stability monitoring, and strengthening of SCFB.