In chirality research area, it is of interest to reveal the chiral feature of inorganic nanomaterials and their enantioselective interactions with biomolecules. Although common Raman spectroscopy is not regarded as a direct chirality analysis tool, it is in fact effective and sensitive to study the enantioselectivity phenomena, which is demonstrated by the enantio-discrimination of amino acid enantiomers using the polydopamine-modified intrinsically chiral SiO2 nanofibers in this work. The Raman scattering intensities of an enantiomer of cysteine are more than twice as high as those of the other enantiomer with opposite handedness. Similar results were also found in the cases of cystine, phenylalanine, and tryptophan enantiomers. In turn, these organic molecules could be used as chirality indicators for SiO2, which was clarified by the unique Raman spectra-derived mirror-image relationships. Thus, an indirect chirality detection method for inorganic nanomaterials was developed.