Hybrid energy storage systems (HESS) combine different energy storage technologies aiming at overall system performance and lifetime improvement compared to a single technology system. In this work, control combinations for a vanadium redox flow battery (VRFB, 5/60 kW/kWh) and a lithium-ion battery (LIB, 3.3/9.8 kW/kWh) are investigated for the design of a HESS. Four real-time energy management/power allocation scenarios are considered for the operation of the hybrid storage solution through a 15-year economic and energetic analysis. The results obtained for each scenario are compared with a single technology battery performance. In the definition of the scenarios, real electricity generation is considered from two solar photovoltaic installations (3.2 kWp and 6.7 kWp) and an estimated representative load of a services building. HESS performance is evaluated through specific energy and economic key performance indicators. The results obtained indicate that the use of customized energy management strategies (EMSs) renders the VRFB and LIB characteristics complementary, besides enhancing the competitiveness of VRFB, as a single technology. Moreover, the HESS management impacts the seasonality factor, contributing to the overall electric system smart management.