Collaborative problem solving (CPS), as a twenty-first century skill, is critically important for both living and life-long learning. Motivation in CPS equates to students' needs to recognize their efforts in collaboration. Given the complexity of CPS contexts, the intertwined relationship among different types of motivations was investigated using a person-centred approach to identify different configural profiles of collaborators based on PSI ([psi]) theory. A total of 9398 Chinese students in 264 schools were included in this study. Latent profile analysis was used to identify four profiles of students with different CPS motivations: "Achievement-oriented cooperator" (n = 773), "Instrument-oriented Cooperator" (n = 1539), "Achievement-oriented nonteam player" (n = 1202), and "Instrument-oriented nonteam player" (n = 5884). Their psychological attributes and CPS behaviours were further analysed, with the following results: (1) achievement-oriented cooperators performed the best, while instrument-oriented nonteam players performed the worst; and (2) students who are achievement-oriented and value collaboration with others are more likely to engage in CPS tasks. These findings provide insights into how different motivational configurations influence CPS behaviours, offering practical implications for enhancing collaboration in educational settings.