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Laser frequency combs, with their unique combination of precisely defined spectral lines and broad bandwidth, are a powerful tool for basic and applied spectroscopy. Here, we report offset-free, mid-infrared frequency combs and dual-comb spectroscopy through supercontinuum generation in silicon-on-sapphire waveguides. We leverage robust fabrication and geometrical dispersion engineering of nanophotonic waveguides for multi-band, coherent frequency combs spanning 70 THz in the mid-infrared (2.5 μm–6.2 μm). Precise waveguide fabrication provides significant spectral broadening with engineered spectra targeted at specific mid-infrared bands. We characterize the relative-intensity-noise of different bands and show that the measured levels do not pose any limitation for spectroscopy applications. Additionally, we use the fabricated photonic devices to demonstrate dual-comb spectroscopy of a carbonyl sulfide gas sample at 5 μm. This work forms the technological basis for applications such as point sensors for fundamental spectroscopy, atmospheric chemistry, trace and hazardous gas detection, and biological microscopy.