Surface‐sensitive UV Raman spectroscopy is used to analyze the crystallinity of silicon films less than 20 nm thick directly on silicon wafers. The 325‐nm excitation has a Raman detection thickness of only 13 nm within the silicon film, thus eliminating signal from the substrate. We demonstrate measured crystallinities of microcrystalline silicon thin films that are consistent with the microstructure observed in transmission electron microscopy. Comparison is also made to ellipsometry, which is less able to accurately determine crystallinity than UV Raman spectroscopy. The UV Raman approach is particularly useful for layers grown on substrates of the same material but with different microstructure, and can be extended to non‐silicon materials.