Existing research has demonstrated that problematic smartphone use (PSU) may reflect a composition of heterogeneous symptoms, with individual PSU symptoms uniquely related to predisposing variables. The Big Five personality traits represent one of the most frequently examined predisposing variables in relation to PSU. However, no studies to date have examined the trait-to-symptom association between the Big Five personality traits and PSU. Using a network analysis approach, we aimed to understand: 1) specific pathways linking each of the Big Five personality traits to PSU symptoms and 2) the bridging effects of each Big Five personality trait on the PSU symptom cluster. A regularised graphical Gaussian model was estimated among 1,849 Chinese university students. PSU symptoms were assessed with items from the Problematic Smartphone Use Scale. Facets of the Big Five personality traits were assessed with the subscales of the Chinese Big Five Personality Inventory-15. An empirical index (i.e., bridge expected influence) was used to quantify bridge nodes. Results revealed specific and distinct pathways between the Big Five personality traits and PSU symptoms (e.g., Neuroticism-Escapism/Avoidance, Conscientiousness-Preoccupation and Extraversion-Escapism/Avoidance). Further, Neuroticism showed the highest positive bridge centrality among the Big Five personality traits, while Conscientiousness had the highest negative bridge centrality. The current study provided direct empirical evidence concerning specific pathways between the Big Five personality traits and PSU symptoms and highlighted the influential role of Neuroticism and Conscientiousness as potential targets for early detection and treatment of PSU.