Ultrabroadband electro-optic sampling using few-optical-cycle probing pulses is a sensitive technique to detect electric field amplitudes with a high dynamic range and up to near-infrared optical frequencies. By combining this method with dual-frequency-comb spectroscopy and using a new class of ultrafast lasers, we perform high-resolution, 80 MHz/0.0027 cm−1 (10 MHz/0.0003 cm−1 with spectral interleaving), spectroscopic measurements in the frequency range 1.5–45 THz (6.6–200 µm), excluding the strongly absorbing Reststrahlen band of lattice resonances at 4.5–9 THz, with an instantaneous spectral coverage exceeding an octave (e.g., 9–22 μm). As a driving source, we use a pair of mutually coherent combs from Kerr-lens mode-locked solid-state Cr:ZnS (2.35 μm) lasers. One of the combs is frequency downconverted via intrapulse difference frequency generation to produce a longwave “sensing” comb, while the second comb is frequency doubled to produce a near-IR “probe” comb for electro-optic sampling (EOS). The low intensity and phase noise of our dual-comb system allow for capturing a large amount of spectral information (200 000 comb-mode-resolved spectral lines spaced by 80 MHz) in the mid-IR portion of the spectrum at a video rate of 69 Hz, with the signal-to-noise ratio limited by the shot noise of the near-IR EOS balanced detection system. Our dual-comb spectroscopy measurements with low-pressure gaseous ethanol, isoprene, and dimethyl sulfide reveal Doppler-limited spectroscopic signatures that have never been explored before.