Engineering cellular microenvironments with biomaterials is an effective strategy for endothelial cell expansion and functionality in vascular tissue engineering. The basement membrane (BM) is a natural vascular endothelium microenvironment that plays an important role in promoting rapid expansion and function of endothelial cells. However, mimicking the crucial function of BM with an ideal biomaterial remains challenging. In this study, we developed a cell-derived decellularized extracellular matrix (c-dECM) paper to mimic the role of BM in endothelial cell expansion and function. The results showed that c-dECM paper was a stable, biocompatible, and biodegradable scaffold that significantly promoted endothelial cell expansion by modulating cell migration, adhesion, and proliferation both in vivo and in vitro. Moreover, the biomimetic c-dECM paper can profoundly promote endothelial cell function by increasing the synthesis and release of nitric oxide (NO) and prostaglandin I2 (PGI2) and upregulating the expression of anticoagulant and vascularized genes, including thrombomodulin (THBD), tissue factor pathway inhibitor (TFPI), endothelial growth factor (VEGF) and endoglin (CD105). These data indicate that the c-dECM is a potential biomaterial for constructing vascular tissue engineering scaffolds or developing in vitro models to study the functional mechanisms of endothelial cells.