Pulsed Laser Deposition (PLD) was used to prepare thin fi lms with the nominal composition La 0.58 Sr 0.4 Co 0.2 Fe 0.8 O 3− δ (LSCF). The thin fi lm microstructure was investigated as a function of PLD deposition parameters such as: substrate temperature, ambient gas pressure, target-to-substrate distance, laser fl uence and frequency. It was found that the ambient gas pressure and the substrate temperature are the key PLD process parameters determining the thin fi lm micro-and nanostructure. A map of the LSCF fi lm nanostructures is presented as a function of substrate temperature (25-700 ° C) and oxygen background pressure (0.013-0.4 mbar), with fi lm structures ranging from fully dense to highly porous. Fully crystalline, dense, and crack-free LSCF fi lms with a thickness of 300 nm were obtained at an oxygen pressure lower than 0.13 mbar at a temperature of 600 ° C. The obtained knowledge on the structure allows for tailoring of perovskite thin fi lm nanostructure, e.g., for solid oxide fuel cell cathodes. A simple geometrical model is proposed, allowing estimation of the catalytic active surface area of the prepared thin fi lms. It is shown that voids at columnar grain boundaries can result in an increase of the surface area by approximately 25 times, when compared to dense fl at fi lms.