This naturally occurring quasi-experiment examined how learning goal orientation (LGO), delivery mode (classroom vs. blended learning), and the perception of barriers and enablers related to motivation to learn and course outcomes. Study participants were 600 students enrolled in either classroom or blended learning courses. As hypothesized, learners in the blended learning condition, high in LGO, and who perceived environmental features as enablers rather than barriers had significantly higher motivation to learn. Motivation to learn, in turn, was significantly related to course outcomes (satisfaction, metacognition, and grades). The mediation hypotheses received partial support. Finally, exploratory analyses revealed 3 significant interactions between delivery mode, LGO, and perceived barriers and enablers on motivation to learn and course satisfaction.