The effects of annealing temperature on microstructures, phase transformation, mechanical properties, and shape memory effect of Ti–20Zr–10Nb–5Al alloy were investigated. X-ray diffraction(XRD) patterns show that the alloy is composed of single hexagonal ɑ’-martensite phase for both as-rolled sample and sample annealed at773 K for 30 min, while single orthorhombic ɑ’’ phase exists in the samples annealed at 873 and 973 K for30 min. The optical observations indicate that the alloy is recrystallized when annealed at 873 K, and the grain size of the sample annealed at 973 K is about five times larger than that annealed at 873 K. Both of the samples annealed at 873 and 973 K show almost the same reverse martensite transformation start temperature of 483 K as demonstrated by thermal dilatation tests. The critical stress values for martensite reorientation(σ_M) are 392 and 438 MPa for the alloys annealed at 873 and 973 K, respectively. The maximum shape memory strain is 2.8 %, which is obtained in the alloy annealed at 873 K due to the lower σ_M. Moreover,the sample annealed at 873 K exhibits larger tensile stress and tensile strain due to the smaller grain size. The effects of annealing temperature on microstructures, phase transformation, mechanical properties, and shape memory effect of Ti-20Zr-10Nb-5Al alloys were investigated. X-ray diffraction (XRD) patterns show that the alloy is composed of single hexagonal ɑ’- martensite phase for both as-rolled sample and sample annealed at 77 K for 30 min, while single orthorhombic ɑ ’’ phase exists in the samples annealed at 873 and 973 K for 30 min. The optical observations indicate that the alloy is recrystallized when annealed at 873 K, and the grain size of the sample annealed at 973 K is about five times larger than that annealed at 873 K. Both of the samples annealed at 873 and 973 K show almost the same reverse martensite transformation start temperature of 483 K as demonstrated by The critical stress values ​​for martensite reorientation (σ_M) are 392 and 438 MPa for the alloys annealed at 873 and 973 K, respectively. The maximum shape memory strain is 2.8%, which the sample annealed at 873 K exhibits larger tensile stress and tensile strain due to the lower grain size.