Abstract The gas metallicity of galaxies is often estimated using strong emission lines such as the optical lines of [O iii] and [O ii]. The most common measure is “R23,” defined as ([O ii]λλ3726, 3729 + [O iii]λλ4959,5007)/Hβ. Most calibrations for these strong-line metallicity indicators are for continuum selected galaxies. We report a new empirical calibration of R23 for extreme emission-line galaxies using a large sample of about 800 star-forming green pea galaxies with reliable T e -based gas-phase metallicity measurements. This sample is assembled from Sloan Digital Sky Survey (SDSS) Data Release 13 with the equivalent width of the line [O iii]λ5007 > 300 Å or the equivalent width of the line Hβ > 100 Å in the redshift range 0.011 < z < 0.411. For galaxies with strong emission lines and large ionization parameter (which manifests as log [O iii]λλ4959,5007/[O ii]λλ3726,3729 ≥0.6), R23 monotonically increases with log(O/H) and the double-value degeneracy is broken. Our calibration provides metallicity estimates that are accurate to within ∼0.14 dex in this regime. Many previous R23 calibrations are found to have bias and large scatter for extreme emission-line galaxies. We give formulae and plots to directly convert R23 and [O iii]λλ4959,5007/[O ii]λλ3726,3729 to log(O/H). Since green peas are best nearby analogs of high-redshift Lyα emitting galaxies, the new calibration offers a good way to estimate the metallicities of both extreme emission-line galaxies and high-redshift Lyα emitting galaxies. We also report on 15 galaxies with metallicities less than 1/12 solar, with the lowest metallicities being 12+log(O/H) = 7.25 and 7.26.