The expansion of mass rapid transit systems such as the metro in urban metropolitan areas is expected to moderate the problems of congestion and public transport overcrowding. It is crucial to devise measures to attract private vehicle commuters towards these modes to make them economically and financially viable. Positive perceptions and high trip frequency of commute trips can lead to long-term habitual inertia and prevent these commuters from shifting towards new sustainable alternatives. To support transport policy-making in promoting sustainable modes, this study mainly investigated the association of private vehicle commuters’ travel wellbeing perception of their commute, commute frequency, and travel attributes with their mode shift behavior towards an upcoming metro system in Mumbai Metropolitan Region (MMR). Some external changes will occur in the transport system regarding time, cost, and other attributes with the upcoming 426 km metro line network in MMR. A well-designed stated preference survey was conducted, and 2400 observations were collected from 217 private vehicle commuters (two-wheelers and cars). Results indicate that the commuters value metro on-board comfort the most, followed by transfers, travel time, and waiting time. Existing travel wellbeing perception is found to be insignificant in determining the mode shift behavior. Furthermore, regular private vehicle commuters showed a significant shifting propensity towards the upcoming metro. Mann-Whiteney U test results indicate no significant differences in travel wellbeing perceptions among car and two-wheeler commuters.