Abstract: Ambidexterity plays an important role in catching up for latecomer firms. However, it is still unclear how the latecomer firms can accomplish the process of catch-up through sequential ambidexterity. The longitudinal case study of CIXING from 1988 to 2018 found that latecomer firms can carry out different organizational learning according to the nature of technological change in the process of technological catch-up. The radical change period of technological paradigm shift is guided by exploratory learning and the independent institutes are responsible for that change. The convergence period of the technical paradigm tends to be stable, which dominated by exploitation and can be completed in mainstream institutions. At the same time, as the technological difficulty of catch-up increases, the R&D team of the firm is upgraded from lightweight to heavyweight. The dynamic matching between the nature of technological change, the type of organizational learning and the internal factors of the organization enables the latecomer firms to oscillate between exploration and exploitation rhythmically, forming sequential ambidexterity, and thus achieved technological catch-up with leading international companies. The conclusions of this paper contributed to the research of technological catch-up and ambidextrous learning.