La-doped manganese oxide catalysts with nanorod morphology, cryptomelane octahedral molecular sieve structure (OMS-2) and La/Mn atomic ratios of 0.0045, 0.0097, and 0.0459 (denoted as La-OMS-2-A, La-OMS-2-B, and La-OMS-2-C) were synthesized with the reaction among KMnO4, La(NO3)3, and Mn(NO3)2 at 90 °C. They were used for photothermocatalytic oxidation of ethyl acetate (typical organic pollutant) merely with UV–visible-infrared (UV–vis-IR) illumination. An appropriate amount of La doping was found to dramatically enhance photothermocatalytic activity and diminish the selectivity of more toxic by-product acetaldehyde. The optimal La-OMS-2-B demonstrated exceptionally large photothermocatalytic activity, low acetaldehyde selectivity, and good catalytic stability. Within initial five minutes, its CO2 formation rate (rCO2) was exceptionally high (1362.0 μmol g−1 min−1), a 67-fold increase as compared to pure OMS-2, while its acetaldehyde selectivity was very low (1.9%), a 37-fold decrease as compared to pure OMS-2. Even with λ > 830 nm IR illumination, it still possessed good photothermocatalytic performance. The photothermocatalytic oxidation abided by a light-driven thermocatalysis mechanism. The dramatic catalytic enhancement by the La-doping arose from a considerable promoted thermocatalytic activity due to the oxygen activity of OMS-2 being substantially improved with La-doping. A photoactivation on La-OMS-2-B, quite unlike photocatalysis on semiconductor photocatalysts, was discovered that further substantially improved catalytic activity and decreased acetaldehyde selectivity due to the oxygen activity of OMS-2 being considerably promoted with UV–vis-IR illumination.