The perovskite La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF48) film was deposited on Crofer 22 APU ferritic stainless steel by pulsed laser deposition (PLD). Morphological studies of the sample were performed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Information about film thickness and surface topography of the film and the steel substrate were obtained using following optical methods: spectroscopic ellipsometry (SE), bidirectional reflection distribution function (BRDF) and total integrated reflectometry (TIS). In particular, the BRDF study, being complementary to atomic force microscopy, yielded information about surface topography. Using the previously mentioned methods, the following statistic surface parameters were determined: root-mean square (rms) roughness and autocorrelation length by determining the power spectral density (PSD) function of surface irregularities.