Since the discovery of the peculiar conducting and optical properties of aromatics, many efforts have been made to characterize and predict their phosphorescence. This physical process is exploited in modern Organic Emitting Light Diodes (OLEDs), and it is also one of the processes decreasing the efficiency of Dye-sensitized solar cells (DSSCs). Herein, we propose a computational strategy for the accurate calculation of singlet-triplet gaps of aromatic compounds, which provides results that are in excellent agreement with available experimental data. Our approach relies on the domain-based local pair natural orbital (DLPNO) variant of the "gold standard" CCSD(T) method. The convergence of our results with respect to the key technical parameters of the calculation, such as the basis set used, the approximations employed in the perturbative triples correction, and the dimension of the PNOs space, was thoroughly discussed.