The present study adds to the evolving literature on green consumer behavior by examining through statistically robust methods the effect and interrelationships of the key constructs of environmental concern, consumer environmental knowledge, beliefs about biofuels, and behavioral intention (i.e., willingness to use and pay) in the context of biofuels. Data were collected through a survey of 1695 respondents. Hypotheses are based on a literature review and a pilot study, and the conceptual structural model developed is tested through structural equation modeling. Results show that concern for the environment has a positive and direct impact on environmental knowledge, beliefs, and behavioral intention. Also, demographics determine levels of concern for the environment and environmental knowledge. All constructs associate positively with one another delineating that the interdependencies between them are important when accounting for environmental behavior. Future research should validate present results with the use of cross‐cultural samples and investigate whether environmental concern increases due to social desirability response bias.