The unique relationship between the value capture mechanism (VCM) and transit-oriented development (TOD) stations and their peripheral areas, which progressively develops an expanded multimodal network, is well acknowledged in the transport industry. However, in regards to the location of TOD stations, insufficient attention has been paid to user travel behaviours and the operating mechanism of the multimodal network. To bridge this research gap, we develop a bi-level programming model for the location of TOD stations that analyses user travel behaviour in the multimodal network. The VCM and transit priority are the objectives of the upper level of this multi-objective optimization model. And the lower level of the model is a modified multimodal network equilibrium based on the Davidson function. Using a simple numerical simulation, this study proposes explanations for some traffic paradoxes from the perspective of a multimodal network equilibrium. We also illustrate competition and collaboration between rail and bus transport systems. Finally, this study uses an empirical case to describe the feasibility and applicability of the model. The results demonstrate that the location of TOD stations is not only one of the keys to the competitiveness of public transport but is also relevant to implementing its VCM.