The chelicerates are a ubiquitous and speciose group of animals that has a considerable ecological effect on modern terrestrial ecosystems—notably as predators of insects and also, for instance, as decomposers1. The fossil record shows that chelicerates diversified early in the marine ecosystems of the Palaeozoic era, by at least the Ordovician period2. However, the timing of chelicerate origins and the type of body plan that characterized the earliest members of this group have remained controversial. Although megacheirans3,4,5 have previously been interpreted as chelicerate-like, and habeliidans6 (including Sanctacaris7,8) have been suggested to belong to their immediate stem lineage, evidence for the specialized feeding appendages (chelicerae) that are diagnostic of the chelicerates has been lacking. Here we use exceptionally well-preserved and abundant fossil material from the middle Cambrian Burgess Shale (Marble Canyon, British Columbia, Canada) to show that Mollisonia plenovenatrix sp. nov. possessed robust but short chelicerae that were placed very anteriorly, between the eyes. This suggests that chelicerae evolved a specialized feeding function early on, possibly as a modification of short antennules. The head also encompasses a pair of large compound eyes, followed by three pairs of long, uniramous walking legs and three pairs of stout, gnathobasic masticatory appendages; this configuration links habeliidans with euchelicerates (‘true’ chelicerates, excluding the sea spiders). The trunk ends in a four-segmented pygidium and bears eleven pairs of identical limbs, each of which is composed of three broad lamellate exopod flaps, and endopods are either reduced or absent. These overlapping exopod flaps resemble euchelicerate book gills, although they lack the diagnostic operculum9. In addition, the eyes of M. plenovenatrix were innervated by three optic neuropils, which strengthens the view that a complex malacostracan-like visual system10,11 might have been plesiomorphic for all crown euarthropods. These fossils thus show that chelicerates arose alongside mandibulates12 as benthic micropredators, at the heart of the Cambrian explosion.