Due to the high vulnerability of the karst aquifer to the surface contaminants, a precisely defined catchment area has the highest priority. In this study, the influence of slope inclination, the doline density analysis, and the water budget analysis in the delineation process of a complex karst catchment area is discussed. To define hydrogeological role of lithological units, cross sections of slope inclination and doline density were combined with hydrogeological cross sections, while the degree of karstification was used to describe the permeability of rock units. The verification of karst catchment delineation area was performed with water budget analysis. The methodology used for the determination of hydrogeological behavior and delineation of a complex karst catchment area (Slunjčica River basin, Croatia) is shown with the flow diagram. It has been found that the highest doline density appears in the range from 0 to 1° of the slope inclinations, and that it decreases with a higher slope degree. Although the results of this study confirm that even with the relatively small number of input data it is possible to define the karst catchment area, it must be emphasized that the doline density analysis presents an indispensable tool in the research related to the definition of karst catchment areas.