Skeletal muscle tissue engineering presents a promising avenue to address the limitations pertaining to the regenerative potential of stem cells in case of injury or damage. The objective of this research was to evaluate the effects of utilizing novel microfibrous scaffolds, containing the compound quercetin (Q), on skeletal muscle regeneration. Morphological test results showed us that the combination of bismuth ferrite (BFO), polycaprolactone (PCL), and Q were bonded and well-ordered with each other, and a uniform microfibrous structure was obtained. Antimicrobial susceptibility testing of PCL/BFO/Q was conducted, and microbial reduction was found to be over 90% in the highest concentration of Q-loaded microfibrous scaffolds with the most inhibitory effect on S. aureus strains. Further, biocompatibility was investigated by performing MTT testing, fluorescence testing, and SEM imaging on mesenchymal stem cells (MSCs) to determine whether they could act as suitable microfibrous scaffolds for skeletal muscle tissue engineering. Incremental changes in the concentration of Q led to increased strength and strain, allowing muscles to withstand stretching during the healing process. In addition, electrically conductive microfibrous scaffolds enhanced the drug release capability by revealing that Q can be released significantly more quickly by applying the appropriate electric field, compared with conventional drug-release techniques. These findings suggest a possible use for PCL/BFO/Q microfibrous scaffolds in skeletal muscle regeneration by demonstrating that the combined action of both guidance biomaterials was more successful than Q itself acting alone.