We study energy harvesting in a binary phononic crystal (PC) beam at the defect mode. Specifically, we consider the placement of a mismatched unit cell related to the excitation point. The mismatched unit cell contains a perfect segment and a geometrically mismatched one with a lower flexural rigidity which serves as a point defect. We show that the strain in the defect PC beam is much larger than those in homogeneous beams with a defect segment. We suggest that the defect segment should be arranged in the first unit cell, but not directly connected to the excitation source, to achieve efficient less-attenuated localized energy harvesting. To harvest the energy, a polyvinylidene fluoride (PVDF) film is attached on top of the mismatched segment. Our numerical and experimental results indicate that the placement of the mismatched segment, which has not been addressed for PC beams under mechanical excitation, plays an important role in efficient energy harvesting based on the defect mode.