In this work, it is analyzed the effect of the partial substitution of Fe by Ni in a BaFeO3 perovskite to be used as the catalyst for NOx-assisted diesel soot oxidation. A series of BaFe1−xNixO3 (x = 0, 0.2, 0.4 and 0.8) catalysts have been synthesized by using the sol–gel method. The catalysts have been characterized by ICP-OES, XRD, XPS, O2-TPD, H2-TPR- and TEM. The catalytic activity for NO to NO2 oxidation and NOx-assisted diesel soot oxidation have been determined by Temperature Programmed Reaction experiments (NOx -TPR and Soot-NOx-TPR, respectively) and by isothermal reaction at 450 °C. Ni seems not to be inserted in the BaFeO3 perovskite and, instead of that, BaNiO3 perovskite and NiO are detected on the surface of the perovskite BaFeO3. XPS data reveal the coexistence of Fe(III) and Fe(IV) on the catalyst’s surface (being Fe(III) the main oxidation state) and the presence of oxygen vacancies. All catalysts are active for NO oxidation to NO2, showing BaFeO3 and BaFe0.6Ni0.4O3 the best catalytic performance. BaFe0.6Ni0.4O3 shows the highest proportion of nickel on surface and it combines the highest activity and stability for NOx-assisted diesel soot oxidation. Also, this catalyst presents the highest initial soot oxidation rate which minimizes the accumulation of unreacted soot during reaction.