Fe-doping in TiO2 has been proven to improve several of its properties, including the photocatalytic activity. Time-differential perturbed angular correlation (TDPAC) as the applied spectroscopy method is particularly interesting because it can probe the electric and magnetic interactions on a local atomic scale. In this work the hyperfine interactions on 111Cd atoms substituting Ti atoms in TiO2 due to nearby Fe atoms also diluted within the TiO2 lattice were measured as a function of temperature. The results review two fractions with distinct quadrupole interaction parameters. One site, occupied by the 111Cd probes, presents the smaller quadrupole interaction frequency, namely υq1 = 45 MHz, and can be ascribed to sites that are more distant from the Fe substitutional site whereas the second site characterized with υq2 = 62 MHz is related to Cd probe atoms that are closer to the Fe defect. Additionally, the system has been characterized using electron dispersive spectroscopy.