The prospective applications of metallic glasses are limited by their lack of ductility, attributed to shear banding inducing catastrophic failure. A concise depiction of the local atomic arrangement (local atomic packing and chemical short‐range order), induced by shear banding, is quintessential to understand the deformation mechanism, however still not clear. An explicit view of the complex interplay of local atomic structure and chemical environment is presented by mapping the atomic arrangements in shear bands (SBs) and in their vicinity in a deformed Vitreloy 105 metallic glass, using the scanning electron diffraction pair distribution function and atom probe tomography. The results experimentally prove that plastic deformation causes a reduction of geometrically favored polyhedral motifs. Localized motifs variations and antisymmetric (bond and chemical) segregation extend for several hundred nanometers from the SB, forming the shear band affected zones. Moreover, the variations within the SB are found both perpendicular and parallel to the SB plane, also observable in the oxidation activity. The knowledge of the structural–chemical changes provides a deeper understanding of the plastic deformation of metallic glasses especially for their functional applications and future improvements.