The invention discloses a quaternary sulfide semiconductor photocatalytic material used for concrete bacteriostasis and corrosion prevention as well as a preparation method and application. The quaternary sulfide semiconductor material is obtained by using alkali carbonate, a transition metal (Mn), a binary solid solution (Sb2S3) and powdered sulfur (S) as raw materials and ammonia water, hydrazine hydrate and polyethylene glycol 400 as solvents to react in an environment at 120-180 DEG C for 5-8 days. The chemical composition formula of the quaternary sulfide semiconductor photocatalytic material is AMn2Sb3S7 (A=K, Rb). The preparation method has the advantages of high synthetic yield, simple operation process, low raw material cost, mild reaction conditions, low synthesis temperature, and the like. Quaternary sulfides obtained by adopting the preparation method have yield of more than 40% and high chemical purity and can be used in the fields of corrosion prevention, bacteriostasis, batteries, catalysis, and the like.