This paper presents the results of annual measurements of the corrosion progress at test samples of cast iron and carbon steel placed in different natural environments. Comparative tests were performed in two outdoor stations, one at the Railway Museum in central Warsaw and one at the location of a Railway Museum in the small town of Sochaczew, 50 km west of Warsaw. The influence of surface roughness on the development of corrosion was determined by two kinds of treatment of all sample surfaces − metal brush or grinding. Stratigraphy and composition of corrosion products in quarterly periods were analyzed with laser-induced breakdown spectroscopy (LIBS) and Raman laser spectroscopy. Comparative tests were performed using a scanning electron microscopy (SEM) system equipped with energy dispersive spectrometer (EDS) and micro-chemical analytical methods. The corrosion layers on carbon steel have proven to be thicker on average than on cast iron, and thicker on the brushed parts of both materials. Furthermore, a thicker corrosion layer was found on the cast iron test samples exposed in Sochaczew than in Warsaw. Different iron oxides, namely lepidocrocite, goethite, hematite and magnetite were identified in the surface Raman spectra of corrosion layers, the last compound only in the sample from Sochaczew. SEM EDS measurements of surface elemental concentrations showed a higher concentration of sulfur in all samples from Sochaczew. Registered LIBS spectra have been additionally analyzed with statistical approach, using Factorial Analysis (FA). Results generally confirmed conclusions drawn from SEM/Raman/LIBS results.