The unique structure and physical properties of perovskite-type catalysts make them highly promising for catalyzing efficient coal combustion. Mesoporous perovskite LaNixFe1−xO3 (x = 0.2, 0.4, 0.6, 0.8) coal combustion catalysts were synthesized using the sol–gel method. The effects of the doping amount of B-site doped nickel on both the crystal structure and catalytic performance were investigated. X-ray diffraction, scanning electron microscopy, and nitrogen adsorption–desorption tests were used to characterize the catalyst samples. Thermogravimetric analysis (TG) and activation energy (Ea) calculations were used to assess the catalyst’s activity for the catalytic combustion of anthracite coal (JF coal, originating from Shanxi, China). Results revealed that nickel doping created lattice distortion and Ni-Fe alloy interactions. The difference in nickel doping significantly affects the morphology and catalytic activity of perovskite. The addition of LaNi0.6Fe0.4O3 (NI6) with a mass fraction of 5% resulted in the highest average burning rate value (va = 4.52%/min) of JF coal among all synthesized catalysts. The Ea of JF coal catalytic combustion, calculated using the Coats–Redfern method and the Doyle method, showed a good agreement with the TG curves. The LaNixFe1-xO3 series catalysts were found to significantly decrease the Ea of JF coal combustion, with a maximum reduction of 42% compared to the case without any catalyst added. Among the synthesized catalysts, NI6 exhibited a favorable catalytic combustion performance and is thus a promising candidate for the clean and efficient utilization of coal resources.