One of the goals of wound repairing is to mimic the function and architecture of the native extracellular matrix (ECM). To this end, for the first time, we used pluronic F127 and mesoporous rod-like hydroxyapatite nanoparticles (mr-HAP NPs) simultaneously to prepare a novel low-diameter electrospun ECM-mimicking wound dressing based on a mixture of chitosan and polyethylene oxide. F127 is used as a surface tension regulator of the polymer solution. In addition, F127 has the special ability to reduce the size of nanofibers. mr-HAP NPs are used as cell proliferation accelerators which also improve the mechanical properties and water uptake capacity of the as-prepared dressing. The average size of nanofibers in the presence of F127 was about 110 nm which was more than 2.5 times lower than nanofibers prepared without F127. The water uptake capacity was evaluated to investigate the wound exudate absorption capacity of the wound dressing. It was observed that the incorporation of mr-HAP NPs into wound dressing structure increases the water uptake capacity by more than 2.5 times. Alongside the evaluation of cytocompatibility through in vitro cell viability assay, the wound healing efficacy was also determined in full-thickness skin wounds in a rat model for 15 days. The cytocompatible wound dressing showed significantly higher wound closure efficacy than the control group so the wounds healed entirely on the last day of the treatment period. As well, the pathology analysis proved better granulation tissue development and greater re-epithelialization. These findings are by virtue of the improved mechanical properties, accelerated cell migration and proliferation, proper environment for oxygen exchange, and enhanced exudate uptake of the wound dressing. These all are due to the presence of F127 and mr-HAP.