In 1982, the “one-child policy” was implemented by China’s Constitution, which led to the majority of post-1990s college students in China being the only child in their family. Unique characteristics have been demonstrated in psychological development of post-1990s Chinese college students due to the lack of sibling companionship, and the relationship between their psychological state and academic performance can affect their future academic sustainability. This paper used Beijing College Students Panel Survey (BCSPS) data to study the role of negative emotions, achievement goals, and academic self-efficacy on academic performance and gives a panoramic description of the China’s post-1990s college students’ psychological states based on the four-year data of more than 2000 college students who enrolled in 2008. We then used regression analysis and a two-way fixed effect model to study the effects of the psychological state on academic performance. The research conclusions of the study are as follows: (1) The levels of negative emotions, achievement goals, and academic self-efficacy vary according to the grade and gender of college students; (2) among all negative emotions discussed, only anxiety presents a significant predictive effect on academic performance, while the effect of stress and depression is not significant; (3) the presence of level of mastery–approach goals is higher than the other three achievement goals, and college students’ academic self-efficacy keeps decreasing from freshman to junior year; (4) performance–approach goals and academic self-efficacy are identified as having a significant promoting effect on academic performance; (5) mastery–avoidance goals and performance–avoidance goals are proven to have a negative effect on academic performance. This paper discusses the contribution of the psychological sustainability and sustainable development to college students’ academic performance from a primary intervention perspective. We believe that it is feasible to improve academic achievement by improving noncognitive factors, such as mental state, to achieve academic sustainability.