Excessive smartphone use has recently become a topic of interest. Prior studies have suggested that psychological well-being variables and motivations are important predictors of excessive smartphone use. However, few have examined the internal mechanism of these factors in leading to excessive smartphone use. Based on Compensatory Internet Use theory, we investigated the moderating role of psychological resilience between two types of motivation — escapism and social interaction — and excessive smartphone use. Selecting 576 typical smartphone users, we found: (1) Escapism motivation and psychological resilience significantly correlate with excessive smartphone use, whereas social interaction motivation does not; (2) Psychological resilience moderates the relationship between both escapism and social interaction motivation and excessive smartphone use. Our study demonstrates the mechanism of different types of motivation and the protective effect of psychological resilience on excessive smartphone use. Thus, we emphasize resilience training that would help train people to be able to cope with life problems more effectively.