The production of electric energy from rivers by using mini, as well as micro hydroelectric power plants, is a very promising solution, especially in rural and isolated areas. Numerous waterways in Croatia and their hydrological and hydrogeological diversity present an opportunity, but also a challenge, for the construction of hydroelectric power plants. Due to the complexity of the water courses’ hydrology, as well as hydrogeological characteristics, it is very hard to determine an appropriate flow pattern (amount), which will be used as an input value for the sizing of hydroelectric power plants. Such analysis will be provided for real case studies in Croatia with special regard to present geological media—media with intergranular porosity (Bednja River), karst media (Gornja Dobra River), and flysch media (Mirna River). Considering different geological media increases the possibility of using the presented methodology on other locations in Croatia, as well in the world. It has been shown that the analyzed rivers definitely have potential for electric energy production, regarding the potential and kinetic river energy. The presented analysis is scientifically original, but also shows the procedure for the determination of the hydro-energy potential of the rivers, as well as for the sizing on the hydropower plants. Hydrology and hydrogeology analyses rounds out the usual hydro-energy analysis, which is in most cases based on basic statistical parameter analysis.