We review our work on combinatorial search and investigation of morphotropic phase boundaries (MPBs) in chemically substituted BiFeO3 (BFO). Utilizing the thin-film composition spread technique, we discovered that rare-earth (RE = Sm, Gd, and Dy) substitution into the A-site of the BFO lattice results in a structural phase transition from the rhombohedral to the orthorhombic phase. At the structural boundary, both the piezoelectric coefficient and the dielectric constant are substantially enhanced. It is also found that the observed MPB behavior can be universally described by the average A-site ionic radius as a critical parameter, indicating that chemical pressure effect due to substitution is the primary cause for the MPB behavior in RE-substituted BFO. Our combinatorial investigations were further extended to the A- and B-site cosubstituted BFO in the pseudoternary composition spread of (Bi1-xSmx)(Fe1-yScy)O-3. Clustering analysis of structural and ferroelectric property data of the fabricated pseudoternary composition spread reveals close correlations between the structural and ferroelectric properties. We show that the evolution in structural and ferroelectric properties is controlled solely by the A-site Sm substitution and not the B-site Sc substitution.