AbstractTernary nitrides are rapidly emerging as promising compounds for optoelectronic and energy conversion applications, yet comparatively little of this vast composition space has been explored. Furthermore, the crystal structures of these compounds can exhibit a significant amount of disorder, the consequences of which are not yet well understood. Here, the deposition of bixbyite‐type ZrTaN3 thin films is demonstrated by reactive magnetron co‐sputtering and observed semiconducting character, with a strong optical absorption onset at 1.8 eV and significant photoactivity, with prospective application as functional photoanodes. It is found that Wyckoff‐site occupancy of cations is a critical factor in determining these beneficial optoelectronic properties. First‐principles calculations show that cation disorder leads to minor deviations in the total energy but modulates the bandgap by 0.5 eV, changing orbital hybridization of valence and conduction band states. In addition to demonstrating that ZrTaN3 is a promising visible light‐absorbing semiconductor and active photoanode material, the findings provide important insights regarding the role of cation ordering on the electronic structure of ternary semiconductors. In particular, it is shown that not only cation order, but also the cationic Wyckoff site occupancy has a substantial impact on key optoelectronic properties, which can guide future design and synthesis of advanced semiconductors.