Active travel (walking or cycling for transport) is considered the most sustainable form of personal transport. Yet its net effects on mobility-related CO₂ emissions are complex and under-researched. Here we collected travel activity data in seven European cities and derived life cycle CO₂ emissions across modes and purposes. Daily mobility-related life cycle CO₂ emissions were 3.2 kgCO₂ per person, with car travel contributing 70% and cycling 1%. Cyclists had 84% lower life cycle CO₂ emissions than non-cyclists. Life cycle CO₂ emissions decreased by −14% per additional cycling trip and decreased by −62% for each avoided car trip. An average person who ‘shifted travel modes’ from car to bike decreased life cycle CO₂ emissions by 3.2 kgCO₂/day. Promoting active travel should be a cornerstone of strategies to meet net zero carbon targets, particularly in urban areas, while also improving public health and quality of urban life.