Although the importance of psychological capital has been firmly supported by prior studies, the question of whether certain subgroups exist and how these various subgroups affect work engagement differentially remains under-explored. To gain an in-depth understanding of this problem, the present study conducted a person-centered method (latent profile analysis) to identify subgroups and then explore the relationship between psychological capital subgroups and work engagement. The study participants were kindergarten teachers in China (n = 2,790). The results showed that psychological capital was divided into three latent profiles: "rich type" (43.2% of the sample) "medium type" (46.3%), and "poor type" (10.5%). Compared to the other two types, the teachers with high psychological capital returned higher work engagement scores. Meanwhile, there was a significant difference among the three identified profiles regarding the location of the kindergarten, the type of kindergarten, and the teaching experience. The group owning more psychological capital tended to have more teaching experience, come from a developed area, and work in a public kindergarten. And after controlling the influence of the type of kindergarten, the location of kindergarten, and the teaching experience, the psychological capital of kindergarten teachers was still an important factor that affected teachers' work engagement.