Previous work has examined how specific personality dimensions are associated with social network characteristics. However, it is unclear how the full range of personality traits relates to the quantity and quality of relationships at different network layers. This study (N = 525) investigates how the six HEXACO personality dimensions relate to the size of support and sympathy groups, and to the level of emotional closeness to network members. Extraversion was positively related to support group size, but did not significantly relate to sympathy group size or emotional closeness. Openness to Experience and Emotionality were positively related to support group size, but not to the size of the sympathy group. Honesty–Humility, but not Agreeableness, was positively related to emotional closeness to members of the sympathy group. Findings suggest that personality effects vary across network layers and highlight the importance of considering both emotional closeness and network size.