Two series of sterically crowded peri-substituted acenaphthenes have been prepared, containing mixed halogen-chalcogen functionalities at the 5,6-positions in A1–A6 (Acenap[X][EPh] (Acenap = acenaphthene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in A7–A12 (Acenap[EPh][E′Ph] (Acenap = acenaphthene-5,6-diyl; E/E′ = S, Se, Te). The related dihalide compounds A13–A16 Acenap[XX′] (XX′ = BrBr, II, IBr, ClCl) have also been prepared. Distortion of the acenaphthene framework away from the ideal was studied as a function of the steric bulk of the interacting halogen and chalcogen atoms occupying the peri-positions. The acenaphthene series experiences a general increase in peri-separation for molecules accommodating heavier congeners and maps the trends observed previously for the analogous naphthalene compounds N1–N12 (Nap[X][EPh], Nap[EPh][E′Ph] (X = Br, I; E/E′ = S, Se, Te). The conformation of the aromatic ring systems and subsequent location of p-type lone-pairs dominates the geometry of the peri-region. The differences in peri-separations observed for compounds adopting differing conformations of the peri-substituted phenyl group can be correlated to the ability of the frontier orbitals of the halogen or chalcogen atoms to take part in attractive or repulsive interactions. Density-functional studies have confirmed these interactions and suggested the onset of formation of three-centre, four-electron bonding under appropriate geometric conditions.