This study aims to explore the impact of industry-university collaboration on enterprises’ intellectual capital. From the perspective of industry-university collaboration relationship management, to explore the influence of different industry-university collaboration relationship on the enterprises’ intellectual capital. Survey was used to collect the data from 406 Zhejiang province hi-tech enterprises’ entrepreneur and senior executives of the industry-university collaboration project using purposive sampling. Quantitative methods were used to analyze the variables and to test hypothesis.Industry-university collaboration itself is a systematic project that needs close collaboration and coordination between the society and relevant units. The relationship between universities and enterprises plays an important role in collaboration. It has become an important obstacle of industry-university collaboration and a restriction factor of knowledge transfer. Therefore, industry-university collaboration cross-organizational management has gradually become a research hotpots for scholars. Taking high-tech enterprises in Zhejiang province as an example, this study studies the different effects of industry-university collaborative relations on enterprises’ intellectual capital from the perspective of industry-university collaborative relations, and improves enterprises’ intellectual capital through scientific and effective management of industry-university collaborative relations. On the basis of Tijssen, Perkmann, Walsh and other research achievements, this study divides the industry-university collaboration into two types of relationship: related type and transactional type. Quantitative research method is adopted to analyze the variables and verify the hypothesis. According to the data analysis results, draw a conclusion: Industry-university collaboration relationship should be based on the related relationship, the enterprise with strong related relationship has higher intellectual capital performance. Finally, according to the research results, some Suggestions on the management of industry-university collaborative relationship are put forward for the reference of local governments and future researchers.