The sudden switch to distance education to contain the outbreak of the COVID-19 pandemic has fundamentally altered adolescents’ lives around the globe. The present research aims to identify psychological characteristics that relate to adolescents’ well-being in terms of positive emotion and intrinsic learning motivation, and key characteristics of their learning behavior in a situation of unplanned, involuntary distance education. Following Self-Determination Theory, experienced competence, autonomy, and relatedness were assumed to relate to active learning behavior (i.e., engagement and persistence), and negatively relate to passive learning behavior (i.e., procrastination), mediated via positive emotion and intrinsic learning motivation. Data were collected via online questionnaires in altogether eight countries from Europe, Asia, and North America (N = 25,305) and comparable results across countries were expected. Experienced competence was consistently found to relate to positive emotion and intrinsic learning motivation, and, in turn, active learning behavior in terms of engagement and persistence. The study results further highlight the role of perceived relatedness for positive emotion. The high proportions of explained variance speak in favor of taking these central results into account when designing distance education in times of COVID-19.