Ferroelectricity in calcium doped hafnium oxide (Ca:HfO2) thin films has been experimentally proved for the first time in this work. All films prepared by chemical solution deposition exhibited smooth and crack-free surfaces, which were observed using an atomic force microscope. After 104 field cycling, a maximum remanent polarization of 10.5 μC/cm2 was achieved in HfO2 films with 4.8 mol. % Ca content. Meanwhile, the breakdown of the film occurred after 7 × 106 electric cycles. A phase transition from the monoclinic phase to cubic/orthorhombic phases was observed with increasing Ca concentration. We suggest the change in oxygen vacancy concentration as the origin of phase evolution, which was confirmed by X-ray photoelectron spectroscopy analysis. These results open a new pathway for realizing ferroelectricity in HfO2-based films.