Since the invention of fluorescent light sources, there is strong interest in Eu3+ activated phosphors as they are able to provide a high color rendering index (CRI) and luminous efficacy, which will also hold for phosphor converted light emitting diodes. Due to an efficient U6+ to Eu3+ energy transfer in Gd3Li3Te2O12:U6+,Eu3+, this inorganic composition shows red photoluminescence peaking at 611 nm. That means Eu3+ photoluminescence can be nicely sensitized via excitation into the U6+ excitation bands. Therefore, photoluminescence properties, such as temperature dependent emission and emission lifetime measurements, are presented. Charge transfer bands were investigated in detail. Additionally, density functional theory calculations reveal the band structure of the pure, i.e., non-doped host material. Obtained theoretical results were evaluated experimentally by the aid of diffuse UV reflectance spectroscopy.