Both the traditional taxi and ridesourcing market provide similar on-demand door-to-door transportation services from the users’ viewpoint, although operate under different legal and regulatory frameworks. Ridesourcing has experienced notable growth in urban mobility in the last few years since it gives a convenient, on-demand door-to-door service, provides app-based real-time information about the trip, and offers flexible prices that vary according to the level of supply and demand at each moment. This new actor in urban mobility directly competes with taxis, a more regulated mode that has traditionally provided door-to-door trips. While competition between taxi and ridesourcing has generated great controversy in the public debate, little attention has been paid to the users’ viewpoint. Additionally, most of the scientific literature on travel behavior and ridesourcing focus on specific characteristics of these services, while scarce efforts have been devoted to study users’ choices and preferences towards ridesourcing vs. its main competitor, taxi services. To bridge this gap, this paper investigates the main factors (individual sociodemographic, mobility-related characteristics, psychological attitudes, etc.) determining individuals’ choices between ridesourcing and traditional taxis. To that end, a Generalized Structural Equation Model (GSEM) is carried out, based on the information collected from a survey campaign conducted in Spain. The results show that, from a behavioral perspective, people opened to technological innovation and with liberal thought (in the sense of being favorable to market openness) tend to use ridesourcing services more often than taxis. Our results also suggest a higher tendency to use ridesourcing among women, young people, and people using hailing services for leisure, recreational or social purposes. Interestingly, individuals having already used both taxi and ridesourcing in Spain, tend to rate higher the quality-of-service performance (driver and/or vehicle fleet) provided by ridesourcing compared to taxis.