It is especially important to solve the psychological pressure of college students’ employment if they want to complete their employment and get better development. This paper proposes a cognitive interaction model based on the full information emotion theory and develops the psychological analysis of employment and entrepreneurial pressure on college students on this basis. In the construction of the cognitive interaction model, the basic assumptions of the all-information affective theory are first proposed, the concepts of the individual’s a priori information, a posteriori information, actual information, and expected information are introduced, the individual’s emotional model is established, and the assumption of information-emotional equivalence is proposed. Combining the PDA model with the information theory of emotional motivation completes the model construction based on this basic assumption. In the model performance test, the accuracy of emotion dimension recognition in this paper’s model is more than 95%, which is better than other models. Taking college students in 2 general colleges and universities in Hunan Province, China, as the research object, the study shows that the total psychological mean score of college students’ employment and entrepreneurship stress is 2.75, and the stress psychology is at a medium level. In the data of the randomly sampled student samples, 70% of the student’s emotional tendencies are anxiety, and anxiety is the mainstream emotion of college students. College students’ feelings of employment and entrepreneurship stress and negative coping styles are both at a high-intensity level.