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Supply chains approaches can be used to solve cayenne pepper-s problems such as unpredictable supply, price fluctuations, uncertainty in production, extreme weather, distribution channels, and price stabilization. Supply chain-s success can be seen from the level of performance. Performance measurement is needed as an approach in order to optimize supply chain networks. The research aims to examine the structure and performance of cayenne pepper supply chain. The study was conducted in Gorontalo and was using survey methods. Data analysis was using descriptive and marketing efficiency analysis. The results showed 1) The structure of the cayenne pepper supply chain in Gorontalo Province consists of seven distribution channels. Sale of cayenne pepper by farmers through collectors (40 percent), wholesalers (26.67 percent), market traiders (10 percent), and retailers (23.33 percent). The primary members of the cayenne supply chain consist of farmers, collectors, wholesalers, out-of-town traders, market traders, retailers, consumers and agroindustries. The secondary members are farm shops, banks, transportation service providers, the Agriculture Service and information media. 2) The most efficient distribution channel is channel six because the smallest marketing efficiency value is 3.17 percent. The cayenne pepper-s market in Gorontalo runs inefficient because it has a price transmission elasticity value of 1.11 (Et> 1). It means the rate of change in prices at the consumer level is greater than the rate of change in prices at the farmers level.