Principal Component Analysis (PCA) is a powerful chemometric tool for the analysis of multivariate datasets. Capitalising from the recent upgrade of the TOSCA spectrometer, we propose to use PCA for the first time to explore phase behaviour in molecular materials. To this end, we have chosen t-butyl chloride, a globular molecule characterised by a rich phase diagram below room temperature, including a low-temperature ordered phase and two plastic-crystalline phases prior to melting. PCA will enable a quantitative analysis of correlations and differences in the proton-projected vibrational densities of states for these four different phases relative to less-abrupt changes of the INS response with temperature. We envisage that this study will pave the way for the analysis of multi-parametric, high-throughput INS data, now within reach using state-of-the-art chemical neutron spectrometers.