Catalysis is the heart of the chemical industry and energy processing. Among the various types of catalysts, heterogeneous catalysts are the most widely used because of their ease of separation from the reaction mixture. Largely owing to the structural heterogeneities of their complex surfaces, most heterogeneous catalytic systems have not yet been fully understood at the atomic level. In many cases, only a limited portion of the surface species determines the overall catalytic performances. Most techniques employed by researchers either provide statistically limited information such as microscopy, or sample-averaged information such as X-ray absorption spectroscopy. From this point of view, site-specific techniques that are capable of providing statistically sufficient information on site identification and quantification as well as the activity evaluation of specific sites are essential. Our research focuses on 1) developing model catalysts to minimize the structural heterogeneities; 2) developing site-specific spectroscopies to distinguish the structures and discriminate the catalytic performance of different sites. The candidate reactions include natural gas conversions (OCM, POM), COx/NOx conversions, selective hydrogenations, metathesis, etc.