MXene has attracted tremendous attention due to its outstanding photothermal properties and biocompatibility. Hydroxyapatite (HA) contains Ca, Mg and P elements, which play important roles in promoting osteogenic differentiation of mesenchymal stem cells (MSCs). In this study, a class of composite nanofibers consisting of MXene nanosheets and HA nanoparticles (M-@HA NFs) are developed based on the synergistic effect of photothermal performance and osteogenic properties. The obtained composite nanofibers demonstrated excellent photothermal properties, and the temperature reached 44 °C under NIR exposure (808 nm). In addition, the composite nanofibers also displayed good biocompatibility and promote the growth and osteogenic differentiation of bone mesenchymal stem cells (BMSCs). More importantly, under NIR exposure, BMSCs on the composite nanofibers achieved much better osteogenic differentiation than those without NIR exposure due to the accelerated release of Ca, Mg and P elements. Therefore, we considered the unique photothermal and osteogenic differentiation to indicate that this new class of MXene composite nanofibers has tremendous application potential in bone tissue engineering.