Despite the rapid accumulation of structural information about organic materials, the correlation between the surface structure of these materials and their chemical properties, a potentially important aspect of their chemistry, is not fully understood. Here, we show that the amorphous or crystalline structure of a solid benzene surface controls its chemical reactivity toward hydrogen. In situ infrared spectroscopy revealed that cold hydrogen atoms can add to an amorphous benzene surface at 20 K to form cyclohexane by tunneling. However, hydrogenation is greatly reduced on crystalline benzene. We suggest that the origin of the high selectivity of this reaction is the large difference in geometric constraints between the amorphous and the crystalline surfaces. The present findings can lead us to a more complete understanding of heterogeneous reaction systems, especially those involving tunneling, as well as to the possibility of nonenergetic surface chemical modification without undesired side reactions or physical processes.