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This study investigated whether a specific set of parents’ social capital—intergenerational closure— associated with Hong Kong students’ science achievement. This study also examined whether the association between intergenerational closure and achievement varies by students’ motivation and self-efficacy on science success. Two-level hierarchical linear models were employed to analyze data from the Programme for International Student Assessment (PISA) 2015. Results revealed that parents’ social interactions with school staff could help Hong Kong students perform better in the subject of science. The educational benefits of parents’ social relationships with school staff were contingent on family socioeconomic status and students’ science self-efficacy. The results provide insights to improve student’s achievement for other regions and Hong Kong in particular.