In this paper, we show how the composition of bimetallic Fe-Ni exsolution can be controlled by the nature and concentration of oxygen vacancies in the parental matrix and how this is used to modify the performance of CO2-assisted ethane conversion. Mesoporous A-sitedeficient La0.4Sr0.6-alpha Ti0.6Fe0.35Ni0.05O3 +/-delta (0 < alpha < 0.2) perovskites with substantial specific surface area (>40 m2/g) enabled fast exsolution kinetics (T < 500 degrees C, t < 1 h) of bimetallic Fe-Ni nanoparticles of increasing size (3-10 nm). Through the application of a multitechnique concentration of oxygen vacancies associated with iron, which controlled the Fe reduction. Instead of homogeneous bimetallic nanoparticles, the increasing Fe fraction from 37 to 57% led to the emergence of bimodal Fe/Ni3Fe systems. Catalytic tests showed superior stability of our catalysts with respect to commercial Ni/Al2O3. Ethane reforming was found to be the favored pathway, but an increase in selectivity toward ethane dehydrogenation occurred for the systems with a low metallic Fe fraction. The chance to control the reduction and growth processes of bimetallic exsolution offers interesting prospects for the design of advanced catalysts based on bimodal nanoparticle heterostructures.