The study reported in this chapter had a twofold aim. First, this study aimed to test the relationships between academic achievement and academic self-concept based on the extended internal/external frame of reference (I/E) model (Marsh, Kong, & Hau, 2001) with a sample of Chinese vocational students. Second, this study moved forward to test this model by incorporating recent advances in the multidimensional structure of academic self-concept (i.e., its domain-specific structure and a further separation between competence-affect components within each domain). Participants were over 900 Year one vocational students in mainland China. The structural equation modeling (SEM) approach was adopted in analysing the data. In line with previous research, the domain-specific relationship between academic achievement and academic self-concept was supported. A further analysis by separating competence and affect components within each domain of academic self-concept in the I/E model showed that these paths from math, Chinese and English achievements to matching affect self-perceptions were stronger than those paths to corresponding competence self-perceptions. To some extent, these patterns differ from those found in previous studies among students in Western cultures. These interesting findings of the extended I/E model found in Chinese students were discussed in relation to the Chinese cultural model of learning. Implications of the current study for student learning, self-concept research, and school effectiveness are also discussed.