The influence of achievement motives and relational goal structures embedded in schools on learning outcomes as well as their interaction has attracted much attention in educational research. In the secondary multi-level analysis of data from four areas of China (B-S-J-Z) and the United States in the PISA 2018 study, the relationship among students' personal achievement motives (competitiveness, work mastery and fear of failure), competitive or cooperative goal structures in schools, reading achievement and reading self-concept was examined. Results revealed similar relationship across countries: both competitiveness and work mastery motives had positive influence on reading self-concept; competitive goal structure influenced reading achievement. Cross-level interactions were only observed in the Chinese (B-S-J-Z) sample, with the competitive goal structure negatively moderating the relationship between work mastery motive and learning outcomes as well as the relationship between competitiveness motive and self-concept. Implications for theory and educational practice were discussed.