In the modern economies, knowledge becomes the crucial resource and learning is the most important process. The main challenge for enterprise in innovation strategy is how to use knowledge to sustain its continuous innovation. During this strategic search, the most importance task is to recognize and make efficient use of the complementarity among the enterprise’s different learning activities. Based on Lundvall et al.’s distinction between STI learning and DUI learning, this study discusses the correlation between STI learning and DUI learning and their effect on technological innovation performance. After in-depth theoretical analysis, the hypotheses are tested empirically with survey data from 230 Chinese manufacturing firms. The following results are obtained: (1) both STI learning and DUI learning could facilitate enterprise’s technological innovation performance; (2) STI learning and DUI learning are mutual interaction, and they influence innovation performance interactively. Firms combining STI and DUI learning are more likely to innovate than those emphasizing on STI learning or DUI learning respectively; (3) the combination of STI and DUI learning effect not only on the number of new products, but also on new products development speed, originality, development sustainability, and the ratio of new products sales.