The Large Hadron Collider forward (LHCf) experiment was motivated to understand the hadronic interaction processes relevant to cosmic-ray air shower development. We have developed radiation-hard detectors with the use of Gd2SiO5 (GSO) scintillators for proton-proton √s = 13 TeV collisions. Calibration of such detectors for photon measurement has been completed at the CERN SPS T2-H4 line in 2015 using electron beams of 100–250 GeV and muon beams of 150–250 GeV . After the channel-by-channel absolute energy calibration, the energy resolution of the calorimeters is confirmed to be better than 3% for electrons with energy above 100 GeV . The position dependence of the energy scale of the calorimeters was reduced to the level of 1% after the corrections for scintillator nonuniformity and the shower leakage effect. The position resolution of the new shower imaging detector, a GSO-bar hodoscope interleaved in the calorimeter, was 100 μm for 200 GeV electrons. The experimental results are well explained by Monte Carlo simulations. We have confirmed that the new detectors meet the requirement of the LHCf experiment at √s = 13 TeV.