The family of polycyclic aromatic hydrocarbons (PAHs) are versatile building blocks for conjugated materials and can be applied in molecular electronics. Pyrenes are known as the best organic chromophores, and pyrene itself is known as an electron donor, being the properties of pyrene-4,5,9,10-tetraone extensively reported. Likewise quinones are promising electrode materials for lithium-ion batteries (LIBs), but their structure–electrochemical property relationship still remains unclear. The aim of this theoretical study is to disentangle the structural influence on the electrochemical properties of chalcogen derivatives of pyrene-4,5,9,10-tetraone. The calculations were performed with the hybrid functional B3LYP using LANL2DZ basis for the following compounds: pyrene-4,5,9,10-tetrathione, pyrene-4,5,9,10-tetraselenone and pyrene-4,5,9,10-tetratellurone and comparing the results with those of pyrene-4,5,9,10-tetraone. The results obtained indicate that the sulfur derivative is a suitable candidate to carry out experimental studies, since although those of selenium and tellurium compounds also present better prospects than 4,5,9,10-tetraoxopyrene, they require the improvement of available synthetic techniques or even the discovery of new ones.