Inflammation or infectious wound could produce high level of hydrogen peroxide (H2O2), which may prevent wound healing process. It could be directly monitored the generated H2O2 to determine the wound microenvironment, which related to its healing status. Europium(III) Coordination Polymers (Eu CPs) had the ability to detect the level of H2O2 and promote wound healing. Thus, a H2O2-responsive smart dressing, fabricated by loading Eu CPs into polyacrylonitrile (PAN) nanofiber mats, has been presented in this study. This theranostic wound dressing can monitor H2O2 level of the wound microenvironment through a simple visible color change. In addition, in vitro cytocompatibility experiments showed that human umbilical vein endothelial cells (HUVEC) and fibroblast cells (L929) could adhesion and proliferation well onto PAN-Eu CPs nanofiber mats, and the RT-qPCR and western blots results indicated that the mats could promote the expression of angiogenic-related genes and factors by HUVEC. Moreover, in vivo animal tests indicated that PAN-Eu CPs nanofiber mats could effectively accelerated wound healing by promoting neovascularization performed by immunohistochemical analysis. Overall, the smart dressing will understand the information of wound microenvironment and reduce the frequency of dressing change, in turn, saving the healthcare cost as well as reducing patient's stress and pain.