Silicone oil samples were characterized by supercritical fluid chromatography (SFC), matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS), and their off-line combination. SFC was used to separate samples of silicone oils on micropacked capillary columns. The fractions for the identification studies were obtained from SFC runs at defined time intervals, when the restrictor was pulled out from the chromatographic flame ionization detector (FID) and inserted into a glass vial with acetone. MALDI-TOF MS was used for the identification of individual oligomers in the fractions separated. The molecular mass distributions determined based on SFC and MALDI-TOF MS measurements were compared. From this comparison, it follows that the results are in good agreement. However, certain differences were observed: MALDI-TOF MS was capable of detecting somewhat larger oligomers than the SFC-FID, but the lower molecular mass oligomers were not present in the MALDI spectra. Differences in the region of lower molecular masses can be explained by evaporation of the more volatile low molecular mass oligomers resulting from heating of the sample during the MALDI-TOF MS measurements as a result of the absorption of the laser shot energy. The fact that no high mass discrimination effects of the MALDI-TOF MS measurements, compared with SFC, were observed is very promising for further applications of MALDI-TOF MS in characterizing synthetic polymers of moderate polydispersity.