Analysis of commodity chains has provided important insights on how power, resource and market access mediate the distribution of benefits and risks. Given this analytical potential, Commodity Chain Analysis (CCA) is now being applied to the study of biofuels and carbon markets to gain systematic insight into the circumstances, relationships and transformations involved in their production and exchange. By building on and adapting this approach to three distinct case studies (biofuels in Madagascar and forest carbon in Cambodia and Laos), this article contributes new insights on the emergence of value within market environmentalism. The analysis highlights methodological challenges in applying CCA to commodified forms of nature, and the significance of knowledge and value negotiations. All three cases illustrate that it remains highly uncertain whether or not market exchange can ultimately be realized. As in the case of traditional commodities, pre-existing conditions of power and access shape modes of production and network configuration. Parallel and intersecting commodity networks (e.g. for land and timber) also require us to think beyond the traditional single-commodity focus. Thus, we call for an expanded analytical focus in applying CCA to non-material ‘green’ commodities that places greater emphasis on value negotiations and connections within new ‘commodity frontiers’.