An important aspect of the off-grid utilization of hybrid generation systems is the integration of energy storage facilities into their structures, which allows for improved power supply reliability. However, this results in a significant increase in the cost of such systems. Therefore, it is justified to use optimization resulting in the minimization of the selected economic indicator taking into account the most important technical constraints. For this reason, this work proposes an algorithm to optimize the structure of a hybrid off-grid power distribution system (with electrochemical energy storage), designed to supply a load with known daily energy demand. The authors recommend genetic algorithm utilization as well as a modified criterion for evaluating the quality of solutions based on the Levelized Cost of Energy (LCOE) index. Several technical and economic analyses were presented, including unit costs, power distribution of the wind and solar sections, nominal battery capacity, SSSI index (System Self-Sufficiency Index), etc. The model of the system includes durability of the elements which have a significant impact on the periodic battery replacement. The tests were carried out for two types of loads and two types of electrochemical batteries (NMC—Lithium Nickel Manganese Cobalt Oxide; and PbO2—Lead-Acid Battery), taking into account the forecast of an increased lifetime of NMC type batteries and decreasing their price within five years. The proposed synthesis method of photovoltaic-wind (PV-wind) hybrid off-line systems leads to limiting the energy capacity of electrochemical storages. Based on the analyses, the authors proposed recommended methods to improve (reduce) the value of the criterion index (LCOE) for PV-wind off-grid systems while maintaining the assumed level of power supply reliability.