Researchers have acknowledged the importance of guanxi networks for Chinese managers’ performance, but only a few related empirical studies have been carried out. Likewise, even though interpersonal affection has been highlighted as the key to long-term interpersonal interaction, very few studies have explored the relationship between particularistic ties and interpersonal affection in the context of manager networks. We asked 121 high-level managers to enumerate the critical people within their management network. Based on the 745 pairs of network ties acquired, we probed the effect of particularistic ties on interpersonal affection (including affective trust and closeness). We also examined the mediating effect of deep psychological fitness (including similarity in values and interests) and the moderating effect of formal working relationships on particularistic ties and interpersonal affection. Findings include the following: (1) The effect of particularistic ties on interpersonal affection is stronger than that of demographic homophily, and different types of particularistic ties have different effects on interpersonal affection; (2) Deep-level psychological fitness have a significant effect on interpersonal affection; (3) Except for relationships with family members, the effect of particularistic ties on interpersonal affection is mediated by deep-level psychological fitness; (4) For the influence of relationships with family members, past supervisors, and past colleagues on interpersonal affection, the manager’s formal working relationship with important others have a moderated effect. Based on these findings, the actual content of guanxi in the context of Chinese organizations is: (1) the importance of particularistic ties (family, friend, supervisors, colleagues) on interpersonal interaction and affection is much more significant than that of demographic homophily; (2) supervisor’s particularistic ties and affectionate relationships with important others demonstrate the concentric circles’ differential mode of association as per Fei Xiaotong’s theoey; (3) deep psychological fitness is incapable of completely mediating the effects of family ties on interpersonal affection, which is a manifestation of the superiority of family ties in Chinese interpersonal affection; (4) the mediation effect of formal relationships and particularistic ties within organizations reveals the complexity and omnipresence of Chinese guanxi. The limitations of this study and direction for future studies are discussed.