The influence of technological learning on industry-level catch-up has long drawn substantial attention in the catch-up research field. However, the underlying mechanisms of technological learning and the unique catch-up context in large emerging economies are much less explored. To explain the technological learning processes of latecomers that face the technology gap and strive to build differentiated competitive advantage, this study builds on the absorptive capacity perspective and deconstructs technological learning processes into two mechanisms: technology decomposition and technology recombination. The former entails decomposing advanced technologies into pieces, parts, or modules, while the latter entails the process of capturing market opportunities through recombining knowledge from diverse sources into commercial products through localized innovations and adaptations. Then, we propose a unique ‘ladder-like’ catch-up context (i.e., technology ladder and market ladder) and investigate how the technological learning process and the unique catch-up context jointly affect industrial catch-up performance in China. Using seven-year panel data from Chinese manufacturing industries, the results indicate that only technology recombination has a significantly positive relationship with industrial catch-up performance. In addition, the market ladder strengthens the positive impact of technology recombination on industrial catch-up, while the technology ladder weakens the positive impact of technology decomposition on catch-up.