The nuclear quadrupole interaction of the first excited I=1 state of ⁴⁴Sc in the anatase and rutile modifications of bulk TiO₂ was determined by time-differential perturbed-angular correlation of g rays. New LaBr₃(Ce) scintillators with excellent energy resolution allowed us to separate the 68 and 78 keV lines of the g-g cascade. For anatase, an almost axially symmetric electric field gradient (EFG) with an asymmetry parameter of h = 0.10(1) and a nuclear quadrupole frequency of w_Q=9.29(3) Mrad/s was obtained. For rutile, an almost antiaxial EFG with h =0.94(1) and w_Q=16.14(6) Mrad/ s was obtained, which contradicts literature values. Ab initio calculations of the EFG using the WIEN2K code were performed for anatase and rutile for pure systems as well as for relevant impurities, such as Sc and Cd on Ti sites. The nuclear quadrupole moment of the I=1 state in ⁴⁴Sc is redetermined with a sevenfold improved accuracy to be Q = ±0.214(3) b.