This study is pioneer in investigating mode-choice behavior of inter-city traveler for non-business trips in Libya, for this we have successfully developed and validated disaggregate behavioral inter-city non-business travel mode choice model, based on a binary logit structure. Four major inter-city corridors in Libya were the source of the data required for the development of the model. Data was collected based on interviews with 576 respondents. Majority of these data (nearly two-thirds) were used for calibrating the model, whereas, the remaining data were used for validating the model. This study, which is the first of its kind in Libya, investigates the intercity traveler’s mode-choice behavior for non-business trips. The proposed model elucidates car/air transport users’ behavior and investigates their responses to the scenario of enhancing intercity transport. We have also investigated the prospect of car drivers shifting to air transport, based on a case of a diminution in airplane out-of-vehicle travel time (access time to airport, waiting time at airport and egress time from airport). We deem that the findings of this study will facilitate all the levels of decision-makers to sensibly allocate resources for the enhancement of air transportation.