Engineered Cementitious Composite (ECC) was used in the prefabricated shell of a precast composite beam, and the validity of the ECC in the precast monolithic composite beam’s flexural performance was studied. Flexural performance tests were conducted on six specimens to analyze their failure state, failure mechanism, bearing capacity, and deformation capacity. Compared with the Reinforced Concrete (RC) prefabricated shell composite beam, the ECC prefabricated shell composite beam showed a higher bearing capacity and lower damage degree. The yielding load of specimen PSMCB−1 increased by 5.6%. The maximum load of specimen PSMCB−1 reached 256.6 kN, having increased by 8.1%. When the tests stopped, the maximum crack width of specimen PSMCB−1 was 4.1mm, while the maximum crack width of specimen PSMCB−6 reached 9.0 mm. The ECC material in the prefabricated shell also delayed the yielding of the steel bars in the shell.