This study investigates how the use of sustainable transport modes relates to travel satisfaction (general evaluation of travel) and travel affect (emotions during travel) in car-dependent compact cities. Thereby, the study provides evidence on sustainable mobility and travel-related well-being in a context of compact urban form but inadequate provisions for public transport, walking, and cycling. A mixed-methods approach was applied comprising quantitative and qualitative analyses of data from the two major cities of Greece, i.e., Athens and Thessaloniki. Travel satisfaction and travel affect are found to be highest for those who walk for commuting, independently of travel time and other factors. Conversely, travel satisfaction and travel affect are lowest for public transport users, largely due to very long travel times but also poor public transport services in one of the two cities. Results indicate that the experience of traveling by public transport, car, and motorcycle within urban areas greatly depends on transport provision and policies. Overall, findings support the idea that to shift to pleasant, satisfying, and sustainable mobility in car-dependent compact cities, car restrictions should be accompanied by massive improvements in public transport, high-quality walking and cycling infrastructure, and an integrated coordination of different modes.