BiFeO 3 (BFO), a room temperature multiferroic, undergoes a series of structural transformations under varying strain conditions by utilizing appropriate substrates for a specific strain condition. In this study, epitaxial thin films of BFO were grown on La 0.7 Sr 0.3 MnO 3±δ (LSMO), a strain tuning layer on LaAlO 3 [LAO (001)] substrates, using pulsed laser ablation. LSMO layers of varying thicknesses from 2 nm to 20 nm were grown followed by a BFO layer of a fixed thickness (20 nm). A strained layer of ~2 nm thick LSMO stabilizes the tetragonal like phase of BFO. Increasing the thickness of the LSMO layer to 10 nm results in a mixed phase with rhombohedral (R) and tetragonal (T) domains, and a further increment of the LSMO layer thickness to 20 nm stabilizes the rhombohedral phase of BFO. The tetragonal phase with weak monoclinic distortion possessed 180° domains with dominant out-of-plane polarization components. However, the mixed phase (R + T) possessed various plausible polarization components in both out-of-plane and in-plane directions. Further, a thermodynamically consistent model based on the phase field approach was implemented to investigate the role of strain on the formation of domain patterns with various polarization components and piezoelectric coefficients. The simulated domain structure exhibited a similar transformation on the dominant polarization components as observed in experiments across different phases of BFO. Our simulations show that the elastic constraint along the z-direction enhances the tetragonality of BFO. The piezoelectric (d 33 ) coefficient was found to be ~46 pm/V for the 20 nm mixed phase BFO, which was nearly a 200% increment compared to the single phase BFO thin films on LAO. © 2018 Author(s).