This paper constructs a random matrix-based teaching evaluation model for college volleyball clubs and deeply investigates the impact of a random matrix-based teaching evaluation model for college volleyball clubs on the effectiveness of college volleyball teaching. Based on random matrix theory (RMT), we analyze the data characteristics according to the single ring law. By introducing matrix Stein pairs, combined with the Laplace transform method, some concentration inequalities of random matrices are proved, and these inequalities play a very important role in the study of eigenvalues of random matrices. The random matrix model was used to analyze the changes brought by the club-based curriculum teaching to students’ physical quality, and a random matrix-based assessment model of college volleyball club teaching was proposed. The model fit test and independence test were conducted using IBM SPSS Statistics 20 software, and an online survey in the form of Questionnaire Star platform was used to map the correlation between college volleyball education and club-based teaching reform with X college physical education students as the research subjects, to provide more scientific theoretical guidance for the influence of club-based teaching mode of physical education courses on the physical quality of college students.