Bike sharing, as an innovative travel mode featured by mobile internet and sharing, offers a new transport mode for short trips and has a huge positive impact on urban transportation and environmental protection. However, bike-sharing operators face some operational challenges, especially in sustainable development and profitability. Studies show that the customers’ willingness to pay is a key factor affecting bike-sharing companies’ operating conditions. Based on the theories of perceived value, this study conducts an empirical analysis of factors that affect bike-sharing users’ willingness to pay for bike-sharing through measurement scales, user surveys, and structural equation models. We designed a five-point Likert-type scale containing 11 latent variables affecting willingness to pay and a total of 34 measurement items. We investigate bike-sharing users in China’s first and second-tier cities, with a total of 502 participants. The results show that perceived value, payment awareness, trust, and environmental awareness constitute key factors that directly affect bike-sharing users’ willingness to pay. And perceived usefulness, perceived ease-of-use, perceived cost, and perceived risk indirectly affect bike-sharing users’ willingness to pay. However, we found no significant effects of perceived entertainment on perceived value or word of mouth on willingness to pay. Our results are expected to provide theoretical and practical implications for bike-sharing programs.