With the textile industry satisfying steadily increasing consumption levels, excessive usage of valuable natural resources provokes a major environmental footprint: 118 billion cubic meters of water are expected to be utilized for global clothing production in 2030. Therefore, consumers' clothing consumption behavior needs to be shifted towards a more sustainable one. While green purchase behavior in general is well understood, research still lacks a comprehensive approach to explain consumers' purchase behavior of sustainable clothing. To provide a holistic framework which determines the main antecedents of purchase behavior of sustainable clothing and further, to shed light on the gap between purchase intention and subsequent purchase behavior of such clothes, we extended the Theory of Reasoned Action (TRA) approach with well-established constructs from green literature (i.e., perceived environmental knowledge and environmental concerns) and novel constructs derived from prior exploratory findings (i.e., greenwashing concerns, perceived economic risk, and perceived aesthetic risk). Four hundred sixty-four participants were inquired to assess these constructs in the context of sustainable clothing. Our findings indicate that attitude towards sustainable clothing has the highest impact on purchase intention. However, this relation is negatively influenced by consumers' greenwashing concerns. Moreover, we find evidence that consumers’ perceived aesthetic risk negatively impacts the intention-behavior relation, whereas perceived economic risk has no significant effect on this relation.