A great effort has been made to investigate 2D perovskites to improve the stability and controllability in the fabrication of photoelectronic devices. As far as we know, only small organic cations such as methylammonium can incorporate into the multilayered perovskite structure except the cations sandwiched between the inorganic layers. We report here a new layered lead iodide, (H(2)Aepz)(3)Pb4I14) (1), where larger organic cations, bis-protonated 2-(2-aminoethyl)-pyrazole (Aepz), not only were sandwiched between the inorganic layers but also were incorporated within the perovskite-like PbI layered structure. Another 2D compound, (H(2)Aepz)PbI4 (2), was also prepared that was a one-layer perovskite. A simple Schottky device was prepared to investigate the photoelectroresponsive properties of the compounds in comparison with that of a typical organic inorganic hybrid perovskite. In general, the energy gap is decreased with an increase in the perovskite layers, but the band gap of two-layered 1 is larger than that of one-layered 2. The photocurrent densities of the compounds are in the order of 1 < 2 < (CH3NH3)PbI3, which is discussed based on the crystal structures and band energy gaps.