Constructing nanostructures, such as nanopores, within metallic glasses (MGs) holds great promise for further unlocking their electrochemical capabilities. However, the MGs typically exhibit intrinsic atomic-scale isotropy, posing a significant challenge in directly fabricating anisotropic nanostructures using conventional chemical synthesis. Herein a selective leaching approach, which focuses on tailoring the uniformity of atomic ordering, is introduced to achieve pore-engineered Pd-Ni-P MG. This innovative approach significantly boosts the number of exposed active sites, thereby enhancing the electrochemical sensitivity for glucose detection. Electrochemical tests reveal that the nanoporous Pd-Ni-P MG exhibits high sensitivity (3.19 mA mm⁻¹ cm⁻) and remarkable stability (97.7% current retention after 1000 cycles). During electrochemical cycling, synchrotron X-ray pair distribution function and X-ray absorption fine structure analyses reveal that the distance between active sites decreases, enhancing electron transport efficiency, while the medium-range ordered structure of the Pd-Ni-P MG remains stable, contributing to its exceptional glucose sensing capabilities. A microglucose sensor is successfully developed by integrating the nanoporous Pd-Ni-P MG with a screen-printed electrode, demonstrating the practical applicability. This study not only offers a new avenue for the design of highly active nanoporous MGs but also sheds light on the mechanisms behind the high electrochemistry performance of MGs.