The series of eight 5-(TeY)-6-(SePh)acenaphthenes (Y = Fp (2), Tol (3), An-p (4), An-o (5), Tp (6), Mes (7), Tip (8), Nap (9)) were prepared and structurally characterised by X-ray crystallography, solution and solid-state NMR spectroscopy and density functional theory (DFT/B3LYP) calculations. All members of the series, except 5, adopt a BA type configuration comparable to the parent compound 1 (Y = Ph), aligning the Te–C_Y bond along the mean acenaphthene plane and promoting a nonbonded Se⋯Te–C_Y 3c–4e type interaction to form to stabilise the molecule (G-dependence). 5 (Y = An-o) adopts a BC type conformation in the solid but DFT calculations show this optimises to BA. Indication of strong through-space peri-interactions between Te and Se are observed in the ⁷⁷Se and ¹²⁵Te NMR spectra, with J(Te,Se) spin–spin coupling constants (SSCCs) in the range −688 to −748 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin–spin coupling on the same order of magnitude as observed in solution. In order to quantify the steric bulk of the aryl groups (Y), we introduce the crystallographic steric parameter (θ), the cone angle measured from the furthest H atoms lying on the edges of the cone to the Te atom located at its vertex. Modification to Y has no apparent influence over the conformation of the molecule, the degree of molecular distortion occurring in the acenaphthene backbone or the extent of 3c–4e interaction; peri-distances for all eight compounds are within 0.08 Å and no apparent correlation is observed between the steric bulk of Y (θ) and the ⁷⁷Se chemical shifts or J(Te,Se) SSCCs. In contrast, a good correlation is found between θ and ¹²⁵Te chemical shifts. DFT calculations performed on all members of the series confirm the comparable covalent bonding between Te and Se in the series, with WBIs of ca. 0.1 obtained. Natural bond orbital analysis shows a noticeable donor–acceptor interaction between a p-type lone pair on Se and a σ*(Te–C) antibonding orbital, confirming the onset of 3c–4e type bonding.