Abstract: Hexavalent chromium (Cr(VI)) compound is useful to various industries but is toxic and carcinogenic. In this research work, we fabricate an amperometric sensor for the determination of Cr(VI), using a titanium dioxide (TiO₂)-reduced graphene oxide (rGO) composite as the sensing element. The composite was synthesized following sol−gel chemistry, yielding TiO₂ nanoparticles of ~50 nm in size, immobilized on chemically exfoliated rGO sheets. The composite was employed in a 3-electrode electrochemical cell and operated in an amperometric mode, exhibiting good responses to the 50 to 500 ppb Cr(VI). Our best result from pH 3 Mcilvane’s buffer medium reveals the sensitivity of 9.12 × 10⁻⁴ ppb⁻¹ and a detection limit of 6 ppb with no signal interference from 200 ppm Ca(II), 150 ppm Mg(II), and 50 ppb Pb(II). The excellent results of the TiO₂-rGO sensor can be attributed to synergic effects between TiO₂ and rGO, resulting from the presence of n-p heterojunctions and the formation of the TiO₂ nanoparticles on rGO.