Herein, we report the ferroelectricity of HfxZr1–xO2 (HZO) thin films crystallized via excimer laser annealing at 25 °C under atmospheric conditions. We characterized the structure and antiferroelectric/ferroelectric properties of HZO thin films using X-ray diffraction and standard polarization–voltage hysteresis. The laser-annealed Hf0.5Zr0.5O2 thin film was gradually crystallized with increasing laser pulse number. The HZO thin film series exhibited systemic changes in antiferroelectric/ferroelectric properties with variations in Zr concentration. In addition, we constructed a phase diagram of laser-annealed HZO thin films.