While literature in environmental psychology has generally treated values and emotions as separate constructs, research has pointed out that value endorsement and emotional experience are profoundly interconnected processes. Recent studies have shown that the endorsement of environmental values predicted the intensity of the emotions that people experienced towards nature and climate change. Building on these findings, this study investigates whether environmental values may have a role not only in determining the intensity, but also in differentiating the quality of the emotional experience in environmentally-relevant situations. Results showed that in environmentally relevant situations higher centrality of self-transcendence values was selectively associated with the experience of affiliation emotions (i.e., emotions concerning one's relationship with the “other”), while higher activation of self-enhancement values was selectively associated to the experience of both affiliation and achievement (i.e., emotions concerning one's needs and status) positive emotions. These findings advance existing literature by providing first evidence for a systematic link between values and types of emotions experienced in environmentally-relevant situations.