Present work demonstrates, for the first time, the use of multiple probes in a single time differential per-turbed angular correlation (TDPAC) measurement. Two different probes, viz.,¹¹¹In/¹¹¹Cd and ¹⁸¹Hf/¹⁸¹Ta, simul-taneously have been incorporated in both pure rutile and Hafnium (Hf)-doped rutile Titanium Dioxide (TiO₂) sys-tems following a soft chemical method. The rutile structure was identified by the hyperfine parameters, viz., quadru-pole frequency (_^ωQ) and asymmetry (η). Due to the doping of Hf at 5 and 10 at.%, the sample partially lost the purity of the crystal and the fact has been reflected at both the probe sites.