The energy transition toward low-carbon electricity systems has resulted in a steady increase in RESs. The expansion of RESs has been accompanied by a growing number of energy storage systems (ESSs) that smooth the demand curve or improve power quality. However, in order to investigate ESS benefits, it is necessary to determine their reliability. This article proposes a four-state reliability model of a battery ESS operating with a PV system for low-voltage grid end users: households and offices. The model assumes an integration scenario of an ESS and a PV system to maximize autoconsumption and determine generation reliability related to energy availability. The paper uses a simulation approach and proposes many variants of power source and storage capacity. Formulas to calculate the reliability parameters—the intensity of transition λ, resident time Ti, or stationary probabilities—are provided. The results show that increasing the BESS capacity above 80% of daily energy consumption does not improve the availability probability, but it may lead to an unnecessary cost increase; doubling the PV system capacity results in a decrease in the unavailability probability by almost half. The analysis of the results by season shows that it is impossible to achieve a high level of BESS reliability in winter in temperate climates.