In this paper, we present results from the spectropolarimetric follow-up of photometrically selected candidate magnetic B stars from the MOBSTER (Magnetic OB[A] Stars with TESS: probing their Evolutionary and Rotational properties) project. Out of four observed targets, one (HD 38170) is found to host a detectable surface magnetic field, with a maximum longitudinal field measurement of 105 ± 14 G. This star is chemically peculiar and classified as an α² CVn variable. Its detection validates the use of the Transiting Exoplanet Survey Satellite (TESS) to perform a photometric selection of magnetic candidates. Furthermore, upper limits on the strength of a putative dipolar magnetic field are derived for the remaining three stars, and we report the discovery of a previously unknown spectroscopic binary system, HD 25709. Finally, we use our non-detections as case studies to further inform the criteria to be used for the selection of a larger sample of stars to be followed up using high-resolution spectropolarimetry.