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Increasing SOFC electrode's surface area by modification of its microstructure is a well-known technique to reduce electrode polarization resistance. This is because reduced grain size and increased porosity promote diffusion and surface reactions, thus improving the electrode performance. However, a modified microstructure also causes differences in phase stability and in chemical compatibility with other SOFC materials. In this work, we study the effect of particle size in both the electrode performance and the phase stability under different fuel conditions and temperatures. SrTi0.3Fe0.7O3−δ (STF) is both prepared via solid state reaction (STF-SSR) and also by an alternative sol-gel route (STF-SG). The sintering temperature is reduced dramatically with the sol-gel method, hence inducing a higher porosity and a much smaller grain size. As particle size is reduced the stability under fuel conditions is also diminished, so decomposition induced by segregation of metallic Fe and SrO occurs at lower temperatures for the STF-SG sample. The stability under reducing conditions is studied by combined techniques such as TGA, TPR, XRD, SEM and TEM. Performance as anode and cathode is evaluated by Electrochemical Impedance Spectroscopy (EIS) by using electrolyte supported symmetrical cells. Prior to electrochemical experiments, the reactivity between La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM) electrolyte and STF was studied, and also between STF and a Lanthanum Doped Ceria (LDC) buffer layer. It is seen that microstructure also plays a key role in the chemical stability of the STF. The impact of particle size reduction is higher for the anodic polarization resistance, which is reduced twice from STF-SSR to STF-SG.