Nano-sized perovskites were synthesized in a spray flame from nitrate precursors dissolved in ethanol and in ethanol/2-ethylhexanoic acid (2-EHA) mixtures. Experiments with ethanol led to a broad particle-size distribution and to the formation of undesired phases such as La 2 CoO 4 , La 2 O 3 , and Co 3 O 4. The addition of 2-EHA can initiate micro explosions of the burning droplets and has been systematically investigated toward the formation of single-phase, high-surface-area LaCoO 3 and LaFeO 3 with a narrow size distribution. To investigate the effect of 2-EHA, temperaturedependent changes of the chemical composition of the precursor solutions were analyzed with ATR-FTIR between 23 and 70 C. In all cases, the formation of esters was identified while in the solutions containing iron, additional formation of carboxylates was observed. The synthesized materials were characterized by BET SSA, XRD, SAED and EDX-TEM and their catalytic activity was analyzed, reaching 50% CO conversion at temperatures below 160 and 300 C for LaCoO 3 and LaFeO 3 , respectively.