The Late Pleistocene Campanian Ignimbrite (CI) super-eruption (Southern Italy) is the largest known volcanic event in the Mediterranean area. The CI tephra is widely dispersed through western Eurasia and occurs in close stratigraphic association with significant palaeoclimatic and Palaeolithic cultural events. Here we present new high-precision 14C (34.29 ± 0.09 14C kyr BP, 1σ) and 40Ar/39Ar (39.85 ± 0.14 ka, 95% confidence level) dating results for the age of the CI eruption, which substantially improve upon or augment previous age determinations and permit fuller exploitation of the chronological potential of the CI tephra marker. These results provide a robust pair of 14C and 40Ar/39Ar ages for refining both the radiocarbon calibration curve and the Late Pleistocene time-scale at ca. 40 ka. In addition, these new age constraints provide compelling chronological evidence for the significance of the combined influence of the CI eruption and Heinrich Event 4 on European climate and potentially evolutionary processes of the Early Upper Palaeolithic.