AbstractConcern for the environment is prevalent among luxury consumers, and sustainable development has become a pervasive theme in the luxury industry. However, there has been limited empirical research on the burgeoning area of sustainable luxury to profile the characteristics of sustainable luxury consumers. In this research, we explore how value perceptions impact consumers' purchase intentions for sustainable luxury products by building an integrated predictive framework based on the theory of consumption values. We deploy a hybrid partial least squares structural equation modeling–artificial neural network approach with additional importance‐performance map analyses to study a sample of 894 luxury consumers in the United States. The empirical findings show that sustainable luxury is profoundly value‐driven. After accounting for linear and nonlinear patterns, functional, emotional, epistemic, conditional, and green consumption values exhibit significant positive impacts on purchase intention, with the exception of social value. Further, we elucidate a theoretically grounded mediator (conspicuous ethical self‐identity) and a moderator (green advertising receptivity) that buffer the link between consumption values and purchase intention. We also uncover cross‐generational disparities, in which millennials—compared to Gen X—display greater conspicuous ethical self‐identity as well as higher levels of green advertising receptivity and purchase intention. From a theoretical perspective, this research contributes to sustainability marketing literature and advances our understanding of the psychographic, behavioral, and demographic factors that influence sustainable luxury consumption. On a managerial basis, this research offers insights for luxury brand practitioners on how to leverage multidimensional value perceptions in their sustainable product positioning and communication strategies.