Overview: Carbon monoxide (CO) is predicted to be the dominant carbon-bearing molecule in giant planet atmospheres, and, along with water, is important for discerning the oxygen and therefore carbon-to-oxygen ratio of these planets. The fundamental absorption mode of CO has a broad double-branched structure composed of many individual absorption lines from 4.3 to 5.1 µm, which can now be spectroscopically measured with JWST. Here we present a technique for detecting the rotational sub-band structure of CO at medium resolution with the NIRSpec G395H instrument. We use a single transit observation of the hot Jupiter WASP-39b from the JWST Transiting Exoplanet Community Early Release Science (JTEC ERS) program at the native resolution of the instrument (R ~ 2700) to resolve the CO absorption structure. We robustly detect absorption by CO, with an increase in transit depth of 264 \(\pm\) 68 ppm, in agreement with the predicted CO contribution from the best-fit model at low resolution. This detection confirms our theoretical expectations that CO is the dominant carbon-bearing molecule in WASP-39b's atmosphere, and further supports the conclusions of low C/O and super-solar metallicities presented in the JTEC ERS papers for WASP-39b.