Learning maladjustment is a common phenomenon in the context of examination-oriented education system in china, especially among high school students who experience intense pressure when preparing for the national college entrance examination. Previous literature suggests that shyness may negatively affect ones’ cognition, emotion, and behavioral performance and lead to academic and social maladjustment. Therefore, learning adjustment among shy high school students is a critical and practical point of inquiry. With a sample of 677 Chinese senior high school students, this study aims to assess the association between shyness and learning adjustment and related mechanisms of goal orientation (i.e., mastery-approach goals, mastery-avoid goals, performance-approach goals, and performance-avoid goals) and academic help seeking (i.e., instrumental help seeking from teacher, instrumental help seeking from classmate, executive help seeking, and avoidance of help seeking). Self-report measures were adopted to collect information on: demographic characteristics, the level of shyness, goal orientation, academic help seeking, and learning adjustment. Results indicated that shyness was negatively correlated with learning adjustment, and this association was mediated by the dimensions of goal orientation and dimensions of academic help seeking. Specifically, shyness not only predicted learning adjustment through mastery-approach goals, and instrumental help seeking (teachers) but also predicted learning adjustment through the multiple mediating effects of the dimensions of goal orientation and the dimensions of academic help seeking (i.e., mastery-approach goals and instrumental help seeking from teachers, mastery-approach goals and executive help seeking, mastery-avoid goals and instrumental help seeking from classmates, mastery-avoid goals and executive help seeking, and performance-avoid goals and executive help seeking). Identifying these mediators further enables us to work out effective measures to promote shy high school students’ learning adjustment.