California’s climate is characterized by the largest precipitation and streamflow variability observed within the conterminous US This, combined with chronic groundwater overdraft of 0.6–3.5 km3 yr−1, creates the need to identify additional surface water sources available for groundwater recharge using methods such as agricultural groundwater banking, aquifer storage and recovery, and spreading basins. High-magnitude streamflow, i.e. flow above the 90th percentile, that exceeds environmental flow requirements and current surface water allocations under California water rights, could be a viable source of surface water for groundwater banking. Here, we present a comprehensive analysis of the magnitude, frequency, duration and timing of high-magnitude streamflow (HMF) for 93 stream gauges covering the Sacramento, San Joaquin and Tulare basins in California. The results show that in an average year with HMF approximately 3.2 km3 of high-magnitude flow is exported from the entire Central Valley to the Sacramento-San Joaquin Delta often at times when environmental flow requirements of the Delta and major rivers are exceeded. High-magnitude flow occurs, on average, during 7 and 4.7 out of 10 years in the Sacramento River and the San Joaquin-Tulare Basins, respectively, from just a few storm events (5–7 1-day peak events) lasting for 25–30 days between November and April. The results suggest that there is sufficient unmanaged surface water physically available to mitigate long-term groundwater overdraft in the Central Valley.