The　properties　of　LaCoO3　are　modified　by　a　controllable　P　doping　strategy　via　a　simple　sol-gel　route.　It　is　demonstrated　that　appropriate　P　doping　is　beneficial　for　forming　a　relatively　pure　perovskite　phase　and　hinders　the　growth　of　perovskite　nanoparticles.　The　combined　results　of　density　functional　theory　(DFT),　extended　X-ray　absorption　fine　structure　(EXAFS),　X-ray　absorption　near-edge　structure　(XANES),　temperature-programmed　reduction　of　hydrogen　(H-2-TPR),　X-ray　photoelectron　spectroscopy　(XPS),　and　temperature-programmed　desorption　of　ammonia　(NH3-TPD)　reveal　that　appropriate　P　doping　gives　rise　to　more　oxygen　vacancies,　optimized　distribution　of　Co　ions,　and　improved　surface　acidity,　which　are　beneficial　for　the　adsorption　of　active　oxygen　species　and　the　activation　of　propane　molecules,　resulting　in　an　excellent　catalytic　oxidation　performance.　Especially,　LaCo0.97P0.03O3　exhibits　more　surface-active　oxygen　species,　higher　bulk　Co3+　proportion,　increased　surface　Co2+　species,　and　increased　acidity,　resulting　in　its　superior　propane　oxidation　performance,　which　is　dominated　by　the　Langmuir-Hinshelwood　mechanism.　In　situ　diffuse　reflectance　infrared　Fourier　transform　spectroscopy　(DRIFTS)　confirms　that　the　presence　of　P　will　accelerate　oxygen　mobility,　which　in　turn　promotes　the　oxidation　rate.　Moreover,　the　obtained　LaCo0.97P0.03O3　catalyst　displays　excellent　thermal　stability　during　the　60　h　durability　test　at　400　degrees　C　and　strong　resistance　against　5　vol　%　H2O　and/or　5　vol　%　CO2　for　prolonged　150　h.