Sensitivity is an essential parameter to gas sensor for the multiple pollutants reality of the current situation. Selective recognition of a certain gas is a research hotspot. In this paper, molecular imprint and design are adopted to solve this hot problem. A highly selective benzene sensor was developed based on molecular imprinting technique (MIT). Organic/inorganic combined MIT was for the first time used to recognize small organic molecule by our group. Ag-LaFeO3 was used as crosslinker, benzene used as template, and then the molecular imprinted Ag- LaFeO3 (MI-AL) with a small dimension was achieved. The structure of the MI-AL is orthogonal perovskite. And then the MI-ALs was printed onto an alumina tube. Subsequently, a high selectivity molecular imprinting benzene gas sensor was obtained. At 125°C, the response to 1 ppm benzene based on the sensor is 18.5, and the response is lower than 5 to the other test gases. The response time and recovery time are 55 s and 40 s, respectively.