The invention discloses an Al-doped Cu-deficient BiCuSeO-based thermoelectric material and a preparation method thereof. The method comprises a step of compounding Bi, Cu, Bi2O3, Se, Al and Al2O3 powders in the weight ratio of Bi:Cu:Bi2O3:Se:Al:Al2O3=(1-x)/3:1-x:(1-x)/3:1:x/3, wherein x is larger than or equal to 0.025 and is smaller than or equal to 0.125, a step of mixing components uniformly toobtain a mixed powder, a step of milling the mixed powder, grinding the mixed powder with an agate mortar, and placing the powder in a drying box for drying to obtain a dry powder, a step of sealingthe dry powder in a vacuum quartz tube, then placing the vacuum quartz tube into a muffle furnace for high-temperature solid phase reaction, breaking the vacuum quartz tube to take a sample powder outafter a sample is cooled with the furnace, grinding the sample powder with the agate mortar, loading the grinded powder into a graphite mold, and placing the graphite mold into a hot-pressing sintering furnace for sintering, and a step of cooling after the sintering, and releasing the mold to obtain the Al-doped Cu-deficient BiCuSeO-based thermoelectric material. The prepared Al-doped Cu-deficient BiCuSeO-based thermoelectric material has the advantages of high purity, low thermal conductivity, high electrical conductivity, good electrical transmission performance, high power factor and highdimensionless thermoelectric figure ZT.