Chalcogen bonding (ChB) interactions involving group 16 elements are of growing interest due to their utility in supramolecular chemistry and catalysis. We present a detailed spectroscopic and theoretical investigation of ChB in a series of telluronium cation and Lewis base cocrystals, using ¹²⁵Te and ³¹P solid-state NMR spectroscopy (SSNMR), single-crystal and powder X-ray diffraction, and Density Functional Theory (DFT)/Natural Localized Molecular Orbital (NLMO) calculations. The ¹²⁵Te chemical shift tensor components correlate strongly with ChB strength and reveal a consistent increase in the δ₁₁ component and chemical shift anisotropy (CSA) span (Ω) with stronger interactions. This contrasts with prior observations in Te­(II) and Se­(II) systems, underscoring the unique behavior of Te­(IV) cations with three σ-holes. Octahedral distortion metrics (ζ, Δ, Σ) are linked to CSA trends, supporting a model in which ChB-induced asymmetry drives tensor orientation. DFT calculations with spin–orbit relativistic corrections reproduce the experimental trend, while NLMO analysis attributes δ₁₁ shifts to specific bonding orbitals and their change in orientation. Our findings demonstrate the sensitivity of ¹²⁵Te SSNMR to subtle structural and electronic variations in ChB systems and establish tensor analysis as a powerful probe of noncovalent interactions in chalcogen cocrystals.