A series of double-perovskite LaAMnNiO6 (A = La, Pr, Sm) catalysts with mesoporous morphology was prepared by a sol–gel method and further applied into photothermal synergistic degradation of gaseous toluene. Transmission electron microscopy and Brunauer–Emmett–Teller characterizations confirmed that double-perovskite LaAMnNiO6 (A = La, Pr, Sm) had obvious mesoporous structure, which can provide a larger specific surface area and further enhancing the reactivity of catalyst. UV-vis and X-ray photoelectron spectroscopy characterization illustrated that LaSmMnNiO6 possessed higher adsorption oxygen content and light absorption capacity, which contribute to the occurrence of catalytic oxidation in the Mars–van Krevelen redox cycle mechanism. A group of active tests showed that the double-perovskite LaSmMnNiO6 catalyst had a lower reaction initiation temperature (starting reaction at 75 °C) and a lower activity temperature of optimal reaction (more than 90% at 255 °C). Moreover, the research on reaction kinetics of the catalyst demonstrated that LaAMnNiO6 (A = La, Pr, Sm) had lower activation energy and thus exhibited better catalytic activity. The results of the study indicate that the double-perovskite LaAMnNiO6 (A = La, Pr, Sm) has broad application prospects in the field of volatile organic pollutant degradation.