Borexino could efficiently distinguish between α and β radiation in its liquid scintillator by the characteristic time profile of its scintillation pulse. This α / β discrimination, first demonstrated on the ton scale in the counting test facility prototype, was used throughout the lifetime of the experiment between 2007 and 2021. With this method, the α events are identified and subtracted from the solar neutrino events similar to β . This is particularly important in liquid scintillators, as the α scintillation is strongly quenched. In Borexino, the prominent Po 210 decay peak was a background in the energy range of electrons scattered from Be 7 solar neutrinos. Optimal α / β discrimination was achieved with a , with a higher ability to leverage the timing information of the scintillation photons detected by the photomultiplier tubes. An event-by-event, high efficiency, stable, and uniform pulse shape discrimination was essential in characterizing the spatial distribution of background in the detector. This benefited most Borexino measurements, including solar neutrinos in the p p chain and the first direct observation of the CNO cycle in the Sun. This paper presents key milestones in α / β discrimination in Borexino as a term of comparison for current and future large liquid scintillator detectors. Published by the American Physical Society 2024