Pulse shape discrimination (PSD) is one of the most distinctive features of liquid scintillators. Since the introduction of the scintillation techniques in the field of particle detection, many studies have been carried out to characterize intrinsic properties of the most common liquid scintillator mixtures in this respect. Several application methods and algorithms able to achieve optimum discrimination performances have been developed. However, the vast majority of these studies have been performed on samples of small dimensions. The Counting Test Facility, prototype of the solar neutrino experiment Borexino, as a 4 ton spherical scintillation detector immersed in 1000 tons of shielding water, represents a unique opportunity to extend the small-sample PSD studies to a large-volume setup. Specifically, in this work we consider two different liquid scintillation mixtures employed in CTF, illustrating for both the PSD characterization results obtained either with the processing of the scintillation waveform through the optimum Gatti's method, or via a more conventional approach based on the charge content of the scintillation tail. The outcomes of this study, while interesting per se, are also of paramount importance in view of the expected Borexino detector performances, where PSD will be an essential tool in the framework of the background rejection strategy needed to achieve the required sensitivity to the solar neutrino signals.