This paper aimed at exploring comfort level (CL) assessment of mode choice and trip chain related to work trips by structural equation model (SEM). A purpose-built questionnaire survey was conducted among 1020 respondents in Dhaka city to collect data regarding users’ perception of selection of travel modes and trip chains. Various types of motorized and non-motorized modes including bus, CNG, tempo, private car, bi-cycle, rickshaw, etc., were considered in this research. Trip chain and mode choice variables included in the survey were selected from various group discussions and expert academicians’ opinions. After developing four different models, the best model with three latent constructs was identified as the key features explicating the CL of mode choice. The three latent variables are mode choice, trip chain, and trip planning. Analysis result indicates that ‘trip planning’ is more influencing than other two. This signifies users emphasize more on whole planning of a trip than trip chain and mode choice individually. In addition, ‘simple home to work and work to home trip’, ‘owning private car’, and ‘monthly travel expenditure’ are found to be the most significant observed variables that influence CL. CL always has a negative relationship with ‘waiting at stations’ and ‘time to reach destination’ which indicates that users do not feel comfortable to waiting at stations and if extra time is needed to reach destination. The results indicate that number of mode change or reduction of transfers within travel route will decrease the CL. Individuals find CL on the bus mode is better compared to CNG, bi-cycle, or rickshaw. The outcomes demonstrate the significant role of ‘destination distance’ and ‘initial waiting time at stations’ while choosing travel mode.