Permanent access to safe drinking water is guaranteed in most industrialized countries, while climate change is turning it into a serious global issue. Knowing how to use the valuable resource water consciously and sustainably requires well-informed and ecologically aware citizens. Environmental education approaches should help develop long-term environmental knowledge, pro-environmental attitudes, and behavior with the overall goal of promoting environmental citizenship. The present study, thus, examines the influence of environmental values on students’ environmental knowledge in a German primary school sample (9–10-year-old students) by providing an authentic, out-of-school learning experience on the topic of fresh water supply. Our approach goes beyond mere correlation analyses by using structural equation modeling (SEM) to measure effects between the two variables. Environmental values were monitored using the Two Major Environmental Values Model (2-MEV) with its two dimensions, Preservation and Utilization of nature. Following a quasi-experimental design, we assessed the learners’ knowledge before (T0), directly after (T1), and six weeks after (T2) module participation. Confirmatory factor analysis verified the two-factor-structure of the 2-MEV. Preservation turned out as a direct positive predictor of pre-knowledge (T0) but did not show any significant effect on post-knowledge (T1) and knowledge retention (T2). Utilization displayed a larger albeit negative direct effect on knowledge across all testing times, especially for pre- and post-knowledge. Our findings shed light on the significant impact of anthropocentric attitudes on knowledge acquisition within primary school samples and provided valuable insights into feasible environmental learning approaches.