Copper(I) iodide (CuI) is the leading inorganic p-type transparent conductor, attracting major attention for its promising optoelectronic properties and facile growth methods, although, commercial uptake is limited due to its as-of-yet insufficient electrical conductivity. Doping CuI with the chalcogens (O, S, Se, Te) is a viable route to tune its electrical conductivity for applications such as in thin film transistors, hole transport layers in solar cells, and transparent thermoelectric generators. The heaviest chalcogen element, Te, is yet to be explored in heavily intrinsically p-type doped CuI at non-alloying concentrations, the subject of the present work. We report the effects of tellurium at the boundary between the doping and alloying regime (up to a maximum of 2.4 % Te) in CuI thin films and investigation the variation in the thermoelectric properties and electronic band structure of the material. Ion implanting tellurium into CuI led to a progressive reduction in the films' work functions from 4.9 eV to 4.5 eV while the ionization potential remained unchanged, measured through photoemission spectrometry. This signified a modulation of the Fermi energy relative to the valence band edge, having a major effect on the materials' electrical conductivity and Seebeck coefficient, the former decreasing by 3 orders of magnitude, while the latter increased by 80 %. We conducted density functional theory (DFT) calculations to elucidate the effect of tellurium doping on the band structure of CuI. Tellurium doping corroborated the shift of Fermi energy, the incorporation of impurity acceptor states deeper into the band gap, in addition to disordering the valence band maximum. This work shows that, the Fermi energy in heavily p-type doped CuI can be moved away from the valence band through Te doping in addition to introducing band disorder, useful for controlling the hosts’ transport properties.