Here, we report a skeletal nickel catalyst prepared by cumulative processing. The Ni, Al, and CoCrMo multi-component alloys were printed by a dual-powder laser-engineered net-shaping system, and alloy samples with different components were obtained through high-throughput design. After leaching in 5 mol/L NaOH at 40 °C for 2 h, the specific surface area of the catalyst increased with increasing Al content. Increasing the leaching temperature and prolonging the leaching time also effectively increased the specific surface area of the catalyst. After leaching at 80 °C for 12 h, the specific surface area was 42.36 m2/g. After cleaning and hydrogen-reduction treatment at 400 °C, the catalyst showed high catalytic activity. The highest conversion rate of CO reached 89.56%, and the selectivity of CH4 remained above 98% for a long time.