The analysis of the functional properties (ferroelectric, dielectric, and piezoelectric) of chemical solution deposited thin films of the lead-free (Bi0.5Na0.5)1−xBaxTiO3 (BNBT) solid solution prepared from solution precursors with and without Na+ and Bi3+ excesses has been performed in this work. At room temperature a nonergodic relaxor ferroelectric state has been found. The switched polarization of the films is not stable at room temperature, poor remnant polarization, associated with an enhancement of the induced domains randomization produced by the films constraints. The depolarization temperature for the switched polarization allowed us to build up a tentative phase diagram for these BNBT films. Both the better functional properties and the agreement of the depolarization temperature with the freezing temperature of the relaxor Volger–Fulcher behavior permit to locate the center of the morphotropic phase boundary region close to x = 0.055 in the stoichiometric films and x = 0.10 for the films with Na+ and Bi3+ excesses. Based on these results, the possible applications of these films are discussed.