Zinc ions have shown promising osteogenic activity, while silicon ions promote angiogenesis. In this study, we investigated the effects of silicon doping, zinc doping, and their co‐doping on the physicochemical properties, as well as the in vitro angiogenic and osteogenic activities of β‐tricalcium phosphate (β‐TCP). Our findings revealed that silicon doping primarily occurred on the P1 site, leading to lattice stability disruption in β‐TCP and favoring its transformation into α‐tricalcium phosphate (α‐TCP). Notably, a significant portion of silicon ions distributed on the particle surface. As a result, silicon‐doped TCP (Si‐TCP) exhibited remarkable in vitro mineralization activity. Conversely, zinc doping contributed to stabilizing the β‐TCP phase, even at a sintering temperature of 1200 °C, preventing the formation of α‐TCP. Silicon/zinc co‐doped TCP (Si/Zn‐TCP) displayed comparable physicochemical properties to zinc‐doped TCP (Zn‐TCP), thus demonstrating higher thermal stability than pure β‐TCP. Cell response evaluations indicated excellent biocompatibility for Si‐TCP, Zn‐TCP, and Si/Zn‐TCP. Silicon doping significantly enhanced in vitro angiogenic capability, while zinc doping notably improved osteogenic potential of β‐TCP. Furthermore, the bi‐functional ion co‐doping approach in Si/Zn‐TCP resulted in combined angiogenic promoting from Si‐TCP and osteogenic stimulation from Zn‐TCP. These results highlight the considerable potential of Si/Zn‐TCP for bone defect repair applications.This article is protected by copyright. All rights reserved.