In recent years, the widespread availability of Wi-Fi in various settings, including universities, enterprises, and large shopping centers, has become increasingly prevalent. The user’s time and location information embedded in wireless network systems can reveal individual and group social relationships, which indirectly reflect each person’s psychological well-being. However, due to challenges in obtaining complete data, the high complexity of related data, and the absence of suitable data analysis models, few studies have analyzed student social behavior using data from university campus networks. This paper employs real-world data from a renowned Chinese university’s wireless campus network for in-depth analysis and introduces a novel multiangle semantic trajectory similarity (MA-STS) algorithm to infer the intimacy and relationship types (such as teacher-student, friends, classmates, or romantic partners) between users. The experiments demonstrate that the proposed algorithm achieves an accuracy of over 95%.