In environmental literature it is argued that three different value orientations may be relevant for understanding environmental beliefs and intentions: egoistic, altruistic, and biospheric. Until now, the distinction between altruistic and biospheric value orientations has hardly been supported empirically. In this article, three studies are reported aimed to examine whether an egoistic, altruistic, and biospheric value orientation can indeed be distinguished empirically by using an adapted value instrument. Also, it is examined whether these value orientations are differently and uniquely related to general and specific beliefs and behavioral intention. Results provide support for the reliability and validity of the value instrument. All studies replicated the distinction into three value orientations, with sufficient internal consistency. Furthermore, when altruistic and biospheric goals conflict, they seem to provide a distinct basis for proenvironmental intentions. The value instrument could therefore be useful to better understand relationships between values, beliefs, and intentions related to environmentally significant behavior.