The invention discloses a preparation method of a Fe5Ni4S8 hydrogen evolution electro-catalytic material. The method comprises the following specific steps: weighing nano iron powder, nano nickel powder and sulfur powder; adding absolute ethyl alcohol and grinding; uniformly putting the mixture into a mortar and transferring the mortar into a tubular furnace; sealing the pipeline, introducing nitrogen, cleaning the quartz tube for 20 minutes, performing heating to 700 DEG C at a heating rate of 5 DEG C/min, keeping the temperature for 3 hours, performing heating to 1100 DEG C at the same heating rate, keeping the temperature for 10 hours, performing annealing to room temperature, taking out the mixture, uniformly grinding the obtained sample, adding ethanol, and carrying out ball milling for 10 hours by using a planetary ball mill. According to the method, vacuum cladding operation is replaced by nitrogen atmosphere calcination; a quartz ampoule tube and a vacuum sealing machine whichare required by vacuum cladding are not required; and meanwhile, the experiment risk possibly caused by high sulfur pressure is also avoided due to the circulating gas atmosphere, the microcosmic sizeof the sample reaches the nanometer level due to the added ball milling operation after calcination, the active sites on the surface of the sample are increased, and the electro-catalytic hydrogen evolution performance is improved.