Undoped and Eu-doped CaZrO3 crystals were synthesized by the xenon lamp floating zone method, and photoluminescence (PL) and scintillation properties were investigated. The undoped CaZrO3 exhibited a broad PL spectrum peaking at around 410 nm while the Eu-doped CaZrO3 showed some sharp emission lines due to 4f-4f transition of Eu3+. The PL decay time constant of the undoped CaZrO3 was 77.8 ns while the Eu-doped CaZrO3 showed a typical value of 4f-4f transition of Eu3+. In X-ray induced scintillation spectra, undoped CaZrO3 showed a broad emission at 480 nm, and Eu-doped ones exhibited some emission lines at around 600 nm. The afterglow levels of the Eu-doped CaZrO3 were lower than that of the undoped one. •Undoped and Eu-doped CaZrO3 crystals were synthesized by the xenon lamp floating zone method.•Photoluminescence and scintillation properties of CaZrO3 were investigated.•In X-ray induced scintillation spectra, undoped CaZrO3 showed a broad emission at 480 nm.•Eu-doped CaZrO3 exhibited some emission lines at around 600 nm due to 4f–4f transitions of Eu3+ ions.