Traditional tissue engineering scaffolds often serve primarily as passive extracellular matrix (ECM) mimics, lacking the capacity to actively regulate cellular behavior and dynamically engage in complex tissue repair processes. Inspired by the concept of thermal therapy, this study designed and fabricated a photothermal-responsive biomimetic ultrafine fiber scaffold that integrates micro/nano topological structures with localized thermal fields. Using high-precision melt electrowriting, PCL/MXene ultrafine fiber network scaffolds were fabricated with controllable architectures that mimic ECM alignment and may provide topographical cues for cells. Leveraging the photothermal conversion properties of MXene, the scaffold exhibits rapid and stable heating upon near-infrared (NIR) irradiation. Among the tested formulations, the 4 wt% MXene scaffold achieved a favorable balance between printability and photothermal performance, with a photothermal conversion efficiency of 59.4 ± 2.1% and stable temperature control within the mild hyperthermia range (37–42 °C) under cell culture conditions. The scaffold also exhibited concentration-dependent antibacterial activity against Escherichia coli and Staphylococcus aureus (with the 4 wt% scaffold achieving ~99% bacterial reduction), which is consistent with the contact-mediated antibacterial mechanism commonly attributed to MXene nanosheets. In vitro L929 fibroblast studies revealed that under NIR irradiation, the 4 wt% scaffold enhanced cell viability and metabolic activity, suggesting that mild photothermal stimulation promotes cell proliferation. This scaffold design strategy, integrating biomimetic topological cues with dynamic thermal responsiveness, provides insights into the development of photothermal-responsive fibrous scaffolds for tissue engineering applications.