E-scooters aspire to provide flexibility to their users while covering the first/last mile of a multimodal trip. Yet, their dual travel behavior, i.e., utilizing both vehicles’ roadways and pedestrians’ sidewalks, creates new challenges to transport modelers. This study aims to model e-scooter riding behavior in comparison to traditional urban transport modes, namely car and walking. The new modeling approach is based on perceived safety that is influenced by the road environment and affects routing behavior. An ordinal logistic model of perceived safety is applied to classify road links in a 7-point Likert scale. The parametric utility function combines only three basic parameters: time, cost, and perceived safety. First/last mile routing choices are modeled in a test road network developed in Athens, Greece, utilizing the shortest-path algorithm. The proposed modeling approach proved to be useful, as the road environment of an urban area is heterogenous in terms of safety perceptions. Indeed, the model outputs show that the flexibility of e-scooters is limited in practice by their low-perceived safety. To avoid unsafe road environments where motorized traffic dominates, e-scooter riders tend to detour. This decision-making process tool can identify road network discontinuities. Nevertheless, their significance regarding routing behavior should be further discussed.