Economic and environmental concerns over fossil fuels encourage the development of photovoltaic (PV) energy systems. Due to the intermittent nature of solar energy, energy storage is needed in a stand-alone PV system for the purpose of ensuring continuous power flow. Three stand-alone photovoltaic power systems using different energy storage technologies are studied in this paper. Key components including PV modules, fuel cells, electrolyzers, compressors, hydrogen tanks and batteries are modeled in a clear way so as to facilitate the evaluation of the power systems. Based on energy storage technology, a method of ascertaining minimal system configuration is designed to perform the sizing optimization and reveal the correlations between the system cost and the system efficiency. The three hybrid power systems, i.e., photovoltaic/battery (PV/Battery) system, photovoltaic/fuel cell (PV/FC) system, and photovoltaic/fuel cell/battery (PV/FC/Battery) system, are optimized, analyzed and compared. The obtained results indicate that maximizing the system efficiency while minimizing system cost is a multi-objective optimization problem. As a trade-off solution to the problem, the proposed PV/FC/Battery hybrid system is found to be the configuration with lower cost, higher efficiency and less PV modules as compared with either single storage system.