Although there is considerable number of studies on urban travel mode choice, there are still two gaps: we have limited understanding of perceived and attitudinal barriers of sustainable modes and motives of personal car use, and the causes (not correlations) of mode choice decisions are almost unknown for certain geographical contexts such as the Middle East and North Africa (MENA). This study seeks to answer three questions: (1) what are the main barriers to choosing sustainable transport modes like active mobility and public transportation in the Middle East and North Africa? (2) which attitudinal or physical determinants define the transportation mode choice intentions and decisions in Tehran, Istanbul, and Cairo? and (3) what are the differences between the determinants of mode choice decisions in the case cities compared with those of Western societies? In this study, the data collected from 8284 interviewees in Tehran, Istanbul, and Cairo in 2017 were applied in a discrete choice model. The dependent variables of the modeling were the perceived main reasons against walking, biking, and public transit ridership, and the main factor encouraging car-driving. According to the findings, long walking distances, absences or lack of biking infrastructures, social and cultural problems and pressures against biking, and personal preference for cars compared to public transport prevent passengers from walking, biking, and using public transport. Comfort and convenience are the factors that make people avoid public transit in favor of cars. These determinants are fairly different from the main determinants of mode choice decisions in the Western societies. By applying a multinomial logistic regression model, 11 variables related to travel characteristics, perceptions, land-use and neighborhood, socio-economics, and self-selection were found significant or marginally significant in explaining all four models: the barriers to walking, biking, and public transit-use, and the motives for car-use. These findings support the hypothesis of this study that there are differences between the perceived and physical barriers to sustainable mobility as well as the motives of car-use in MENA megacities compared to Western societies. In short, mode-choice decisions and perceived determinants are context-sensitive. The conclusions of this study could be applied in urban and transportation planning in the MENA region to promote more sustainable mobility modes.