High‐pressure synthesis method allows obtaining single‐phase perovskite BiFe1−xScxO3ceramics in the entire concentration range. As‐prepared compositions with xfrom 0.30 to 0.55 have the antipolar orthorhombic Pnmastructure but can be irreversible converted into the polar rhombohedral R3cor the polar orthorhombic Ima2 phase via annealing at ambient pressure. Microstructure defects and large conductivity of the high‐pressure‐synthesized ceramics make it difficult to study and even verify their ferroelectric properties. These obstacles can be overcome using piezoresponse force microscopy (PFM) addressing ferroelectric behavior inside single grains. Herein, the PFM study of the BiFe1−xScxO3ceramics (0.30 ≤ x ≤ 0.50) is reported. The annealed samples show a strong PFM contrast. Switching of domain polarity by an electric field confirms the ferroelectric nature of these samples. The as‐prepared BiFe0.5Sc0.5O3ceramics demonstrate no piezoresponse in accordance with the antipolar character of the Pnmaphase. However, application of a strong enough electric field induces irreversible transition to the ferroelectric state. The as‐prepared BiFe0.7Sc0.3O3ceramics show coexistence of ferroelectric and antiferroelectric grains without poling. It is assumed that mechanical stress caused by the sample polishing can be also a driving force of phase transformation in these materials alongside temperature and external electric field. Polar states in the high‐pressure‐synthesized BiFe1−xScxO3(x= 0.3−0.5) ceramics are addressed via piezoresponse force microscopy. It is proven that the R3cand Ima2 polymorphs obtained by annealing of the as‐prepared ceramics are ferroelectric. In contrast, the as‐prepared Pnmapolymorphs are antiferroelectric but can be irreversible transformed to the ferroelectric state by an electric field or mechanical stress.