The invention provides substituted tricarbonal chloride [2-(2-pyridyl) benzimidazole] co-rhenium complexes or substituted tricarbonal chloride (2,2'-dipyridyl amine) co-rhenium, which are tricarbonal chloride [1-(4-5'-phenyl-1,3,4-oxadiazole phenyl)-2-(2-pyridyl) benzimidazole] co-rhenium (I), tricarbonal chloride [1-(4-N-carbazolyl phenyl)-2-(2-pyridyl) benzimidazole] co-rhenium (I), tricarbonal chloride [N-(4-5'-phenyl-1,3,4-oxadiazole phenyl)-2,2'-dipyridyl amine] rhenium co (I) and tricarbonal chloride [N-(4-N-carbazolyl phenyl)-2,2'-dipyridyl amine] co-rhenium (I). The complexes have a structural formula as follows. The tricarbonal rhenium (I) complexes having the advantages of simple synthesis, help to purification, high yield and stable properties in air can be applied to molecular catalysis, solar energy conversion, colorimetric analysis, molecular recognition, supramolecular assembly, optical information storage, photoluminescence probes in organisms, and other fields. The invention discloses a preparation method for the complexes.