The paper takes urban competitiveness of talents in science and technology as the research object, analyzes the connotation and constituent elements of urban competitiveness of talents in science and technology, and establishes an assessment index system, assesses the competitiveness of talents in science and technology of four municipalities directly under the central government using the comprehensive index method based on AHP. The assessment results show that the competitiveness of talents in science and technology of four municipalities directly under the central government is sorted into Beijing, Shanghai, Tianjin, and Chongqing.