Increasing the electrochemical performance of electrode materials in sodium ion batteries (NIBs) remains a major challenge. Here, a combined experimental and theoretical investigation on the modification induced by Sb2S3 embedded in a heteroatom-doped 3D carbon matrix (CM) for efficient anodes in NIBs is presented. The structural and chemical characterization demonstrates the successful doping of 3D CM with S and Sb atoms. When evaluated as anode materials for NIBs, the heteroatom-doped nanocomposites delivered a better cycling stability and superior rate capability than those of undoped Sb2S3/CM anodes. First principle calculations were used at the Density Functional Theory level to systematically study the Sb2S3/CM and Sb2S3/heteroatom doped-CM composites, as NIBs anodes. Doping the carbon substrate by heteroatoms improved the adsorption of Sb2S3 on the matrix and allowed for ionic/covalent attraction with the Sb2S3 nanoparticle, respectively. Such results could be used to model the stabilty of the composite architectures observed in the experiment, for superior cycling stability. (C) 2020 Elsevier Inc. All rights reserved.