Exploring rapid, sensitive, and multifunctional biosensors is of great significance in medical diagnosis and biotechnology, while creating Cu‐N‐C center‐based enzymatic biodetection system is still a great challenge for colorimetric biosensing fields. Herein, inspired by the axial coordination structure of the natural enzyme, an efficient and specific Cu‐N‐C center‐based peroxidase‐like biocatalyst is created via axial strong‐metal‐support‐interaction (SMSI) between WOx support and Cu‐Nx‐based carbon shell, denoted as Cu‐NC‐WO3. This analysis discloses that the SMSI effect induces electron transfer from Cu to WOx, thus making the valence state of Cu higher and consequently suppressing the O intermediates' adsorption. Owing to this unique structure, the Cu‐NC‐WO3 exhibits exceptional peroxidase (POD) like activities (Km = 3.57 × 10−3 m, Vmax = 13.80 × 10−6 m s−1, and turnover number (TON) = 206.13 × 10−3 s−1 for H2O2), which is more efficient than the other Cu‐Nx center‐based biocatalysts and also many recently reported peroxidase‐like nanomaterials. Meanwhile, this Cu‐NC‐WO3 shows substrate selectivity, low detection limit, and high resistance to extreme environments for abundant H2O2‐related biomarkers, which are revealed by colorimetric studies. Thus, as a helpful method for accurate biodetection, it is believed this work promises to offer rapid, specific, and inexpensive colorimetric biosensors for regions with bare medical resources, as well as new strategies for the structural engineering of enzyme‐like biocatalysts.