BiFeO3 films were grown by RF magnetron sputtering with various O2 gas flow ratios and substrate temperatures. The optimal sputtering conditions for a slightly excess Bi content produced high-quality parameters: an atomically flat surface (Ra < 0.4 nm), low leakage current (Jc < 10–6 A/cm2), high ferroelectric polarization (72 μC/cm2//[001]pc), and large exchange bias (∼140 Oe). In addition to these typical characterizations, the following two advanced analyses were performed: (i) The lattice constant was identified by Bragg’s diffraction specific to a space group of R3c using X-ray diffraction; it was precisely determined as an expanded a-axis (abulk = 0.568 → aepi = 0.572 nm) and a shrunk c-axis (cbulk = 1.398 → cepi = 1.373 nm). (ii) The ferroelectricity was analyzed by first-order reversal curve (FORC) diagrams, which revealed that ferroelectric switching was packed in a narrow electric field area; an internal electric field in the film body was not observed despite the fact that the BiFeO3 films were as-grown samples. A 3 nm thick BiFeO3 film with a continuous and flat surface/interface was confirmed over a wide area. The crystal symmetry might be identified as a space group of R3c in the case of the 3 nm thick film by comparing the nanobeam selected area electron diffraction patterns with the patterns based on structural calculations. The ferroelectricity might be confirmed by the piezoresponse force microscopy of a 2 nm thick BiFeO3 epitaxial film, owing to the optimal condition of low Jc and uniform ferroelectric switching properties. Furthermore, a 0.4 nm thick ultrathin BiFeO3 film was confirmed to be a continuous one-unit cell perovskite (∼0.4 nm) layer, owing to the optimal condition of low Ra. This study provides a method for investigating the crystal symmetry that affects the multiferroic properties of ultrathin films, which can be used as barrier layers in multiferroic tunnel junctions for highly functional sensors.