The present study adopted the structural equation modeling approach to examine Chinese university students’ metacognition, critical thinking skills, and academic writing. In particular, this research explored whether awareness in metacognition can foster critical thinking and, thus, lead to enhancement in academic writing. The measure for exploring metacognitive writing strategies covered metacognitive knowledge and regulation in academic writing. The measure for understanding learners’ critical thinking encompassed the following five skills: inference, recognition of assumptions, deduction, interpretations, and evaluation of arguments. The academic writing assessment was based on an internal test. The participants consisted of 644 third-year students from a Chinese university. Three models tested: (1) the role of metacognition in academic writing; (2) the role of metacognition in critical thinking; and (3) correlations between metacognition, critical thinking skills, and academic writing. The results indicated significant relationships between the three variables, and the implications based on these findings were discussed.