Human capital is one of the most important resources of an enterprise, determining the efficiency of its economic activity. In this regard, forming an adequate system for assessing an enterprise’s human capital is important and relevant. This paper presents an overview of existing approaches for assessing the enterprise’s human capital. The diverse approaches can be grouped into three traditional classes: the income approach, the cost approach, and the market approach. The specifics, advantages and disadvantages of these approaches have been discussed. It is shown that synergetic approach for assessing the enterprise’s human capital allows to reveal new aspects that were not considered in the framework of traditional approaches, and project the trajectory of human capital development. In the framework of the synergetic approach, the human capital of the enterprise is regarded as a complicated system, for which self-organization processes are typical. The self-organization source here is integration of knowledge, which is the basis of human capital, in time and space, and, as a consequence, self-growth of this knowledge. Synergetic approach allows to form the system of the enterprise’s human capital assessment from the standpoint of nonlinear trajectory of its development. In the framework of this approach, human capital is regarded as a complicated self-organizing system. The full extent of the factors affecting its formation and development is considered. It is shown that the graph of knowledge of workers involved directly in the production process allows to characterize relationships between the components of human capital at its different stages, and, as a whole, to give a qualitative representation of the condition of the enterprise’s human capital. Using the synergetic approach for human capital assessment is illustrated with an example of an aircraft manufacturing company. A characteristic of the dynamics of state coordinates is given to describe the functioning of the enterprise from the standpoint of the synergetic approach. We consider the set of knowledge necessary for implementing each stage of the production process as the coordinates of the system state. System condition coordinates are prone to change and to fill with new content due to occurrence of nonlinear system self-organization, i.e., combination of knowledge. The knowledge graph, although it is not directly a cost estimate of human capital, can help to assess acceptability of the basic content of the enterprise’s human capital, and can also be used as a basis for assessing the effectiveness of the enterprise’s human capital management.