Nano-MnO2 was prepared by a sol-gel technology, and the structure was characterized by means of powder X-ray diffraction (XRD). The interaction of dimethyl sulfide (DMS) or ethyl mercaptan (EM) with the as-prepared MnO2 was investigated at ambient temperature with Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and laser Raman spectroscopy (LRS). The results showed that DMS and EM undergo different interactions with the surface of MnO2. The interaction of DMS and MnO2 bring about carbon-sulfur bond cleavage and the oxidation of C. However, there might be hydrogen bonding between EM and MnO2 in addition to chemical bonding, which results in a weaker S-H bond in the EM molecule, so that EM is easily oxidized to sulfonates and sulfates. Tentative interaction mechanisms for DMS and EM on MnO2 are suggested.