Romantic love is a complex state that has been seen as similar to addiction. Previous task-based functional magnetic resonance imaging (fMRI) studies have shown that being in love is closely associated with functional brain changes in the reward and motivation system. However, romantic love-related functional connectivity network organization in resting-state fMRI has yet to be elucidated. To that end, here we used resting-state fMRI and graph theory to compare whole-brain functional network topology between an “in-love” group (n = 34, 16 females, currently in love and in a romantic relationship) and a “single” group (n = 32, 14 females, never in love and not in a romantic relationship). Compared to the single group, we found lower network segregation in the love group (i.e., lower small-worldness, mean clustering coefficient, and modularity), and these metrics were negatively associated with scores on the Passionate Love Scale (PLS) (an index of intense passionate/romantic love). Additionally, the love group displayed altered connectivity degree (reflecting the importance of a node): decreased degree in left angular gyrus and left medial orbitofrontal cortex, but increased degree in left fusiform gyrus. Furthermore, local efficiency or degree of these regions was significantly correlated to PLS scores. Taken together, results showed decreased overall brain functional segregation but enhanced emotional-social processing in romantic lovers. These findings provide the first evidence of love-related brain network organization changes and suggest similar but different brain network alterations between romantic love and addiction, providing new insights on the neural systems underlying romantic love.