This is the first in a series of papers in which we describe and report the analysis of a large survey of Herbig Ae/Be stars in circular spectropolarimetry. Using the ESPaDOnS and Narval high-resolution spectropolarimeters at the Canada–France–Hawaii and Bernard Lyot Telescopes, respectively, we have acquired 132 circularly polarized spectra of 70 Herbig Ae/Be stars and Herbig candidates. The large majority of these spectra are characterized by a resolving power of about 65 000, and a spectral coverage from about 3700 Å to 1 µm. The peak signal-to-noise ratio per CCD pixel ranges from below 100 (for the faintest targets) to over 1000 (for the brightest). The observations were acquired with the primary aim of searching for magnetic fields in...