This paper examines the shifting role of perceived value and satisfaction in the formation of loyalty over the duration of a relationship life cycle. Drawing on a sample of online shoppers in Taiwan, the results show that the association between loyalty intention and shopping experiences conforms to an S-shaped growth curve. Customers’ intentions to stay with a website appear to be influenced by the perceived value and satisfaction formed during the most recent transaction; however, the strength of action inertia gradually declines after the maturity stage. The sample was classified into three segments (i.e., relationship driven and variety seeker; relationship neutral and value seeker; relationship averse and satisfaction seeker), which show distinct behaviors in terms of preferences, relationship status, sex, switching, and e-WOM inclination. Satisfaction is the most powerful driver of loyalty for the first shopping experience. Above and beyond satisfaction, perceived value has a strong impact on motivating new customers to switch from other stores. As for customers with a longer-term relationship with an online store, the effects of perceived value and satisfaction turn out to be moderate. Overall, perceived value and satisfaction have decreasing effects on loyalty in the later stage of a relationship life cycle.