As the cost of photovoltaic (PV) systems and battery energy storage systems (BESS) decreases, PV-plus-BESS applied to behind-the-meter (BTM) market has grown rapidly in recent years. With user time of use rates (TOU) for charging and discharging schedule, it can effectively reduce the electricity expense of users. This research uses the contract capacity of an actual industrial user of 7.5 MW as a research case, and simulates a PV/BESS techno-economic scheme through the HOMER Grid software. Under the condition that the electricity demand is met and the PV power generation is fully used, the aim is to find the most economical PV/BESS capacity allocation and optimal contract capacity scheme. According to the load demand and the electricity price, the analysis shows that the PV system capacity is 8.25 MWp, the BESS capacity is 1.25 MW/3.195 MWh, and the contract capacity can be reduced to 6 MW. The benefits for the economical solution are compared as follows: 20-year project benefit, levelized cost of energy (LCOE), the net present cost (NPC), the internal rate of return (IRR), the return on investment (ROI), discounted payback, total electricity savings, renewable fraction (RF), and the excess electricity fraction. Finally, the sensitivity analysis of the global horizontal irradiation, electricity price, key component cost, and real interest rate will be carried out with the most economical solution by analyzing the impacts and evaluating the economic evaluation indicators. The analysis method of this research can be applied to other utility users to program the economic benefit evaluation of PV/BESS, especially an example for Taiwan’s electricity prices at low levels in the world.