This paper innovatively explores BEV (battery electric vehicle) users’ risk attitudes and charging inertia, examining their effects on en route charging and charging route choice behavior. An attitudinal survey was conducted to explore the two latent variables of risk attitudes and charging inertia in relation to socioeconomic and travel-related characteristics. ICLV (Integrated choice and latent variable) models are adopted to estimate the latent variables and the charging choice behavior simultaneously. Specifically, uncertainty in energy consumption is first considered in the ICLV model, which is represented by the available range (AR) uncertainty. Multinomial logit (MNL) models directly incorporating socioeconomic attributes are employed as a reference for comparison with ICLV models. Results illustrate that risk attitudes and charging inertia both play significant roles in modeling en route charging choice behavior. Risk-averse users and users having charging inertia value AR uncertainty more. Battery range, charging frequency, and income emerge as the most crucial factors influencing users’ intention to charge en route. The results show significant heterogeneity of BEV users in attitudes and charging choice behavior, underscoring the importance of accounting for the heterogeneity in en route charging demand estimation and deployment optimization of public charging stations, particularly for medium-to long-distance trips.