All perovskite p-i-n junction La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3/La0.7Te0.3MnO3 heterostructures were epitaxially deposited on (0 0 1) SrTiO3 substrates. Crystallinities and strain were investigated for p-i-n junction layers. The heterostructures show excellent ferroelectric and switchable domain structures. With the rising temperature, the junctions exhibit a transition from a p-i-n junction (hole/electron) with remarkable diode effect to a p-i-p like junction (hole/small polaron) with a small rectification. The temperature-dependent rectification of p-i-n junctions with 10 nm PZT layer show the consistent trend with that of junctions with 20 nm PZT layer. Our result indicated that the p-i-n junction may provide potential for further research and application.