The ability to probe the molecular fundamental or overtone (high harmonics) vibrations is fundamental to modern healthcare monitoring techniques and sensing technologies since it provides information about the molecular structure. However, since the absorption cross section of molecular vibration overtones is much smaller compared to the absorption cross section of fundamental vibrations, their detection is challenging. Here, a silicon nanostrip rib waveguide structure is proposed for label-free on-chip overtone spectroscopy in near-infrared (NIR). Utilizing the large refractive index contrast (Δn > 2) between the silicon core of the waveguide and the silica substrate, a broadband NIR lightwave can be efficiently guided. We show that the sensitivity for chemical detection is increased by more than 3 orders of magnitude when compared to the evanescent-wave sensing predicted by the numerical model. This spectrometer distinguished several common organic liquids such as N-methylaniline and aniline precisely without any surface modification to the waveguide through the waveguide scanning over the absorption dips in the NIR transmission spectra. Planar NIR Si nanostrip waveguide is a compact sensor that can provide a platform for accurate chemical detection. Our NIR Si nanostrip rib waveguide device can enable the development of sensors for remote, on-site monitoring of chemicals.