The invention discloses a preparation method and application of a carbon-phosphorus-boron ternary co-doped copper/nickel-based catalyst, and the preparation method comprises the following steps: S1, dissolving a copper salt and a nickel salt in deionized water, and magnetically stirring at 50-80 DEG C for 3-5 hours to obtain a mixed solution; s2, adding a catalyst carrier into the mixed solution, performing pressurized impregnation adsorption for 1-3 hours under the pressure condition of 0.5-1.5 MPa, then dropwise adding a 0.02-0.03 mol/L sodium citrate solution, performing stirring reaction for 6-12 hours at the temperature of 20-100 DEG C, filtering, and drying to obtain a composite precursor; s3, placing the composite precursor in a tubular furnace, carrying out heat treatment at 500-600 DEG C for 1-3 hours, then introducing mixed gas of CH4 and PH3 at a flow rate of 250-500 sccm, and carrying out vapor deposition for 2-4 hours to obtain solid particles; and S4, adding the solid particles into a 0.02-0.1 mol/L H3BO3 solution, stirring for 10-20 minutes, controlling the solid-to-liquid ratio to be 1g/10mL, carrying out solid-liquid separation, washing with deionized water for 3 times, and drying, so as to obtain the carbon-phosphorus-boron ternary co-doped copper/nickel-based catalyst. The ZSM-5 molecular sieve is used as a carrier, sodium citrate is used as a metal complexing agent, Cu < 2 + > and Ni < 2 + > grow in situ, non-metallic elements of carbon, phosphorus and boron are deposited, and the selectivity and catalytic activity of the catalyst are improved.