Photothermal therapy (PTT) is a minimally invasive tumor treatment technology, and is regarded as a potential anticancer strategy because of its targeted destruction and low toxicity. Specifically, near-infrared light-induced PTT has attracted intriguing interest because of the high transparency of tissue, blood, and water. However, effective PTT generally requires the assistance of photothermal agents. Gold nanorods (GNRs) and conducting polymer are often used as photothermal materials because of their high absorption efficiency and photothermal conversion efficiency. Herein, we combined GNRs with poly( o-methoxyaniline) (POMA, a polyaniline derivative) to form GNRs/POMA core/shell hybrids through the surfactant-assisted chemical oxidative polymerization route and studied their photothermal conversion properties. The configuration of GNRs/POMA core/shell hybrids has been precisely controlled through adjusting the monomer concentration, and the relationship between morphology and absorption band of GNRs/POMA core/shell hybrids has been revealed. Finally, the in vitro and in vivo experiments were performed, and the results indicated that the GNRs/POMA core/shell hybrids with optimized absorbance at around 808 nm exhibited the best performance on photothermal therapy under 808 nm NIR laser irradiation.