Under the background of the implementation of innovation-driven development strategy and the transformation and upgrading of manufacturing industry, it is of great theoretical and practical significance to study the impact of university-industry collaboration on the technological innovation performance of Chinese manufacturing firms. The effect of university-industry collaboration on the technological innovation performance of firm is analyzed by dividing technological innovation performance into product innovation performance and process innovation performance. The World Bank’s latest survey data of Chinese manufacturing firms and the propensity score matching method are also utilized in the analysis. It is found that university-industry collaboration has a significant positive impact on the technological innovation performance of Chinese manufacturing firms, and its positive impact on product innovation performance is greater than that on process innovation performance. The university-industry collaboration behavior of firms has the characteristics of “self selection”, while the propensity score matching (PSM) method can effectively overcome the sample selection bias and obtain more reliable estimation results. Further heterogeneity analysis shows that the impact of university-industry collaboration on the technological innovation performance of firms of different sizes and ages is heterogeneous.