Focused on the describing resources of the value-creating routine of “relationship finance”, this paper sets up a theoretical model about the relationship among relation-specific investments, VC governance activities and technological innovation on the basis of Resource-based theory and Transaction Cost theory. This paper also discusses the effect of different types of RSI on the technological innovation performance and the mediating role of VC governance activities. The study, which based on the data of the 264 High-tech start-ups, shows that Property-based RSI has positive effect on VC supervision & control and negative influence on VC value-added service while VC supervision & control has negative impact on technological innovation performance. Meanwhile, Knowledge-based RSI is positively related to VC value-added service and negatively related to VC supervision & control while VC value-added service has positive impact on technological innovation performance.