The invention discloses a catalyst for C4 fraction selective hydrogenation and removal of alkyne, and a preparation method thereof. A main metal active component precursor loaded on a carrier and assistant metal component precursors loaded on the carrier are reduced through ionizing radiation to prepared the unsaturated hydrocarbon hydrogenation catalyst provided by the present invention. The main metal active component precursor comprises Pd, wherein the Pd content is 0.01 (wt)%-2.00 (wt)% of the total weight of the carrier. The assistant metal component precursors comprise: (1) at least one selected from Cu, Co, Ag, Cr, Bi, Sn, Pb, Ga, Zn, Sb and Tl, wherein the metal content is 0.005 wt%-30.0 wt% of the total weight of the carrier; (2) optional one or a plurality of metals selected from Na, K, Mg, Ca and Ba, wherein the metal content is 0.005 wt%-5.0 wt% of the total weight of the carrier. The catalyst has advantages of high activity, high selectivity, no requirement of pre-reduction through hydrogen, direct use and the like.