Carsharing services have a significant potential for improving urban mobility by increasing the independence and freedom of travel and reducing traffic externalities. Although carsharing has been used for over a decade, several aspects need further investigation, such as the impact of user’s psychological factors on service use, as well as the factors impacting users’ choices between different carsharing operators, in particular their preferences for different payment schemes, and their perceptions of the operators’ application rating. Accordingly, four hybrid choice models (HCM) were estimated to investigate factors impacting (i) the knowledge about carsharing services, (ii) carsharing adoption, (iii) the shift from other modes to carsharing, (iv) the choice between carsharing operators with different payment schemes, using a large survey sample (N = 1044 responses 9469 SP observation) from Munich, Germany. The models showed the significance of sociodemographics, such as income level, education level, household size, employment status, ownership of a bike, access to a car, the availability of a driving license, and public transport subscription-based tickets on the carsharing use directly and indirectly, and four psychological factors encompassing different personality traits (i.e., adventurous), travel behavior, and attitudes were found to be significant in the various models; the latter covered service-related attitudes (perceived carsharing app importance) and travel behavior attitudes or profiles (frequent public transport user and frequent shared micromobility user). This research raises questions regarding the inequitable use of carsharing, the impacts of mobile applications on using the service, and the potential of integrating carsharing in mobility as a Service platforms to increase the potential for multimodality.