This paper is oriented to the integrated learning bill for college teachers and integrates blockchain technology to construct a high-security and credibility assessment system for college teachers’ professional competence development. Through similarity calculation and hierarchical clustering to form a dataset related to teachers’ professional competence, the TOPSIS-gray correlation analysis algorithm is used to assess the development of teachers’ professional competence tendencies. The teacher information is then transformed to finally form an information profile panel that can comprehensively characterize the development of college teachers’ professional competence, which is stored in the blockchain in the form of a learning bill. The single feature clustering results indicate that the majority of teachers are either good or above in every professional development evaluation feature, with excellent being above 30%. In the overall clustering, only 17.91% were labeled as excellent. In the teacher professional development assessment indicators, the reaction layer (34.9) and learning layer (33.6) have a greater impact on the professional development of teachers in higher education. The F-values of teachers in different subject areas in the overall test of teacher professional development did not reach a significant level (2.11, 0.24, 0.20, and 0.42, respectively). In the correlation test, blockchain technology was significantly and positively correlated with the quality of teachers’ professional development (p<0.05). The validity of the professional development assessment system for college teachers that incorporates blockchain technology is confirmed by this study.