BACKGROUND The nixtamalization process improves the nutritional and technological properties of maize. This process generates nixtamalized maize bran as a by‐product, which is a source of arabinoxylans (AX). AX are polysaccharides constituted of a xylose backbone with mono‐ or di‐arabinose substitutions, which can be ester‐linked to ferulic acid (FA). The present study investigated the fine structural features and antioxidant capacity (AC) of nixtamalized maize bran arabinoxylans (MBAX) to comprehend the structure–radical scavenging capacity relationship in this polysaccharide deeply. RESULTS MBAX presented a molecular weight, intrinsic viscosity, and hydrodynamic radius of 674 kDa, 1.8 dL g−1, and 24.6 nm, respectively. The arabinose‐to‐xylose ratio (A/X) and FA content were 0.74 and 0.25 g kg−1 polysaccharide, respectively. MBAX contained dimers (di‐FA) and trimer (tri‐FA) of FA (0.14 and 0.07 g kg−1 polysaccharide, respectively). The main di‐FA isomer was the 8–5′ structure (80%). Fourier transform infrared spectroscopy confirmed MBAX molecular identity, and the second derivate of the spectral data revealed a band at 958 cm−1 related to the presence of arabinose disubstitution. 1H‐Nuclear magnetic resonance spectroscopy showed mono‐ and di‐arabinose substitution in the xylan backbone with more monosubstituted residues. MBAX registered an AC of 25 and 20 μmol Trolox equivalents g−1 polysaccharide despite a low FA content, using ABTS (2,2′‐azino‐bis‐3‐ethylbenzthiazoline‐6‐sulfonic acid) and DPPH (1,1‐diphenyl‐2‐picrylhydrazyl) methods, respectively. CONCLUSION AC in MBAX could be related to the high A/X ratio (mainly monosubstitution) and the high 8–5′ di‐FA proportion in this polysaccharide. © 2023 Society of Chemical Industry.