The titanium-enriched slag was obtained via atmospheric hydrochloric acid leaching of mechanically activated vanadium titanomagnetite concentrates (VTMCs). Under the influence of mechanical activation, specific physicochemical changes were observed via X-ray diffractometry, scanning electron microscopy, and granulometric laser diffraction analysis. Experimental findings revealed that the mechanical activation of VTMCs resulted in a decrease in the median volume particle diameter (d50) and an increase in the specific surface area (SA) with an increased milling time. The results of the leaching experiment revealed that the mechanical activation treatment favors the extraction of iron (Fe) and titanium dioxide (TiO2) from the VTMCs. The Fe and TiO2 extractions from the mechanically activated sample after 10 h compared with the unactivated sample were increased by 12.82% and 4.73%, respectively. The presence of the ilmenite phase in the titanium-enriched slag was confirmed by X-ray diffractometry and EDS patterns, and the content of the TiO2 in the enriched slag can get as high as 43.75%.