Rectifying and photoelectronic properties of the La0.67Ba0.33MnO3/SrTiO3:Nb junctions with the film thickness from d=0.5 to 30 nm have been systematically studied. It is found that the electronic transport of the junction is dominated by quantum tunneling or thermoionic emission when film thickness is below or above 1 nm. The rectifying ratio and ideality factor, correspondingly, experience a sudden change as film thickness grows from 0.5 to 1 nm and a smooth variation with film thickness above 1 nm. The threshold film thickness for the establishment of a mature depletion layer is therefore 1 nm. The photoemission properties of the junctions also exhibit a strong dependence on film thickness. As experimentally shown, the photocurrent vanishes in the zero thickness limit, and grows rapidly with the increase in film thickness until d=6 nm, where a maximal photocurrent of ∼770 nA/mm2 under the irradiance of the laser of 5 mW and 532 nm is obtained. After this maximum, an increase-to-decrease turning appears with further increasing film thickness. Taking into account the finite diffusion distance of the photocarriers and the strain-enhanced charge trapping in ultrathin film junctions, a theoretical description that well reproduces the experiment results can be obtained, which reveals the severe depression of finite diffusion distance of the extra carriers on photocurrent. The maximal diffusion distance thus obtained is ∼3.5 nm. Similar analyses have been performed for the La0.67Ca0.33MnO3/SrTiO3:Nb junctions, and the corresponding diffusion distance there is ∼1.5 nm.