Millimeter-wave/terahertz rotational spectroscopy of polar gaseous molecules provides a powerful tool for complicated gas mixture analysis. In this paper, a 220-to-320-GHz dual-frequency-comb spectrometer in 65-nm bulk CMOS is presented, along with a systematic analysis on fundamental issues of rotational spectrometer, including the impacts of various noise mechanisms, gas cell, molecular properties, detection sensitivity, etc. Our comb spectrometer, based on a high-parallelism architecture, probes gas sample with 20 comb lines simultaneously. It does not only improve the scanning speed by 20, but also reduces the overall energy consumption to 90 mJ/point with 1 Hz bandwidth (or 0.5 s integration time). With its channelized 100-GHz scanning range and sub-kHz specificity, wide range of molecules can be detected. In the measurements, state-of-the-art total radiated power of 5.2 mW and single sideband noise figure of 14.6-19.5 dB are achieved, which further boost the scanning speed and sensitivity. Finally, spectroscopic measurements for carbonyl sulfide (OCS) and acetonitrile (CH CN) are presented. With a path length of 70 cm and 1 Hz bandwidth, the measured minimum detectable absorption coefficient reaches cm. For OCS that enables a minimum detectable concentration of 11 ppm. The predicted sensitivity for some other molecules reaches ppm level (e.g., 3 ppm for hydrogen cyanide), or 10 ppt level if gas preconcentration with a typical gain of 10 is used.