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The multiple electronic state mechanisms of the reaction of carboryne with benzene were investigated by M11 calculations. Mechanisms leading to [412] cycloaddition product P412, [212] cycloaddition product P212, C-C insert product PC-Cins and CAH insert product PC-Hins were considered. The barrier/stability to structural characteristics correlations revealed that, 1) [212] addition is a two-step mechanism which exhibits three electronic state reactivity, and both the addition steps are controlled by the barriers on open-shell singlet (OSS) potential energy surface (PES); 2) [4+2] product P412 is a kinetic product on the experimental condition, and other products should be obtained under more harsher condition. The theoretical results well explain the experimental facts. [ABSTRACT FROM AUTHOR]