Social networks existing among employees, customers or users of various IT systems have become one of the research areas of growing importance. A social network consists of nodes - social entities and edges linking pairs of nodes. In regular, one-layered social networks, two nodes - i.e. people are connected with a single edge whereas in the multi-layered social networks, there may be many links of different types for a pair of nodes. Nowadays data about people and their interactions, which exists in all social media, provides information about many different types of relationships within one network. Analysing this data one can obtain knowledge not only about the structure and characteristics of the network but also gain understanding about semantic of human relations. Are they direct or not? Do people tend to sustain single or multiple relations with a given person? What types of communication is the most important for them? Answers to these and more questions enable us to draw conclusions about semantic of human interactions. Unfortunately, most of the methods used for social network analysis (SNA) may be applied only to one-layered social networks. Thus, some new structural measures for multi-layered social networks are proposed in the paper, in particular: cross-layer clustering coefficient, cross-layer degree centrality and various versions of multi-layered degree centralities. Authors also investigated the dynamics of multi-layered neighbourhood for five different layers within the social network. The evaluation of the presented concepts on the real-world dataset is presented. The measures proposed in the paper may directly be used to various methods for collective classification, in which nodes are assigned to labels according to their structural input features.