Decarbonization of the power sector is a key step towards greenhouse gas emissions reduction. Due to the intermittent nature of major renewable sources like wind and solar, storage technologies will be critical in the future power grid to accommodate fluctuating generation. The storage systems will need to decouple supply and demand by shifting electrical energy on many different time scales (hourly, daily, and seasonally). Power-to-Gas can contribute on all of these time scales by producing hydrogen via electrolysis during times of excess electrical generation, and generating power with high-efficiency systems like fuel cells when wind and solar are not sufficiently available. Despite lower immediate round-trip efficiency compared to most battery storage systems, the combination of devices used in Power-to-Gas allows independent scaling of power and energy capacities to enable massive and long duration storage. This study develops and applies a model to simulate the power system balance at very high penetration of re-newables. Novelty of the study is the assessment of hydrogen as the primary storage means for balancing energy supply and demand on a large scale: the California power system is analyzed to estimate the needs for electrolyzer and fuel cell systems in 100% renewable scenarios driven by large additions of wind and solar capacities. Results show that the transition requires a massive increase in both generation and storage installations, e.g., a combination of 94 GW of solar PV, 40 GW of wind, and 77 GW of electrolysis systems. A mix of generation technologies appears to reduce the total required capacities with respect to wind-dominated or solar-dominated cases. Hydrogen storage capacity needs are also evaluated and possible alternatives are discussed, including a comparison with battery storage systems. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.