Two-dimensional (2D) heterostructures have shown great potential in advanced photovoltaics due to their restrained carrier recombination, prolonged exciton lifetime and improved light absorption. Herein, a 2D polarized heterostructure is constructed between Janus MoSSe and MoTe2 monolayers and is systematically investigated via first-principles calculations. Electronically, the valence band and conduction band of the MoSSe–MoTe2 (MoSeS–MoTe2) are contributed by MoTe2 and MoSSe layers, respectively, and its bandgap is 0.71 (0.03) eV. A built-in electric field pointing from MoTe2 to MoSSe layers appears at the interface of heterostructures due to the interlayer carrier redistribution. Notably, the band alignment and built-in electric field make it a direct z-scheme heterostructure, benefiting the separation of photogenerated electron-hole pairs. Besides, the electronic structure and interlayer carrier reconstruction can be readily controlled by reversing the electric polarization of the MoSSe layer. Furthermore, the light absorption of the MoSSe/MoTe2 heterostructure is also improved in comparison with the separated monolayers. Consequently, in this work, a new z-scheme polarized heterostructure with polarization-controllable optoelectronic properties is designed for highly efficient optoelectronics.