Single crystalline rutile TiO₂nanorods were prepared by reacting sodium titanate with hydrochloric acid. The proposed formation mechanism involves a growth pathway. The growth proceeds along [001], and the circumferential faces are {110}, which are identified as the photoactive faces of rutile titanium dioxide. Both the heterogeneous (photocatalyst only) and the combined heterogeneous/homogeneous (photocatalyst and H₂O₂) photocatalytic performances support its activity. The mechanism of formation and photocatalytic property are extensively studied.