The electronic and optical responses of an organic semiconductor (OSC) are dictated by the chemistries of the molecular or polymer building blocks and how these chromophores pack in the solid state. Understanding the physicochemical nature of these responses is not only critical for determining the OSC performance for a particular application, but the UV/visible optical response may also be of potential use to determine aspects of the molecular-scale solid-state packing for crystal polymorphs or thin-film morphologies that are difficult to determine otherwise. To probe these relationships, we report the quantum-chemical investigation of a series of trialkyltetrelethynyl acenes (tetrel = silicon or germanium) that adopt the brickwork, slip-stack, or herringbone (HB) packing configurations; the π-conjugated backbones considered here are pentacene and anthradithiophene. For comparison, HB-packed (unsubstituted) pentacene is also included. Density functional theory and GW (single-shot Green's function G and/or screened Coulomb function W) electronic band structures, GW-Bethe-Salpeter equation-derived optical spectra, polarized ϵ spectra, and distributions of both singlet and triplet exciton wave functions are reported. Configurational disorder is also considered. Furthermore, we evaluate the probability of singlet fission in these materials through energy conservation relationships.