Background and Purpose Structuring scaffold with both osteogenic and angiogenesis capabilities is a challenge for bone tissue engineering. Powder structured Si-CaP materials have shown excellent osteogenic properties and induction of stem cell differentiation. Our research group have successful produced 3D printed Si-CaP scaffolds by DLP technology. This study aims to explore the angiogenic effects of SiO32- and Ca2+ released by 3D printed Si-CaP scaffold, and whether there is a synergistic effect between the two ions. Methods The 3D printed Si-CaP scaffolds were immersed in endothelial cell medium solution for 24 h. The Si, Ca ion released was detected by Inductively coupled plasma–optical emission spectrometry. We used detected data as a standard to prepare the simulated solution to investigate the effect of SiO32-, Ca2+ separately. Experiment was divided into control group, Si ion group, Ca ion group and Si + Ca ion group. We evaluated different ionic effect on HUVECs viability, proliferation, migration, gene expression, and tube formation on different groups. Results The concentration of SiO32- was detected as 15.71 ± 0.04 μg/mL, Ca2+ as 67.14 ± 0.95 μg/mL. Na2SiO3 and CaCl2 were used to prepare the simulated solution. There were no statistically difference between simulated solution from ion released by scaffold. Si + Ca group promoted the gene expression significantly compared with the control group, p < .01. Expression of vascular-associated protein in Si + Ca ion group was higher than that in Si ion group, Ca ion group and control group. Si + Ca ion group significantly enhanced endothelial cell on migration and tube formation assay. Conclusion The 3D printed Si-CaP scaffold can release effective physiological concentrations of Si, Ca ions. Si and Ca ions have a synergistic effect on promoting angiogenesis of HUVECs. 3D printed Si-CaP scaffold is promising in vascularized bone tissue engineering application.