Low-dimensional halide organic perovskites formed by introducing larger organic amine groups into the perovskite structure provide a unique opportunity to control charge dynamics for various optoelectronic applications via the independent tuning of the energy levels of the perovskite sublattice and the organic spacers. Nevertheless, 1D perovskites suffer from high exciton binding energy, poor charge carrier separation, and transport efficiencies which degrade their optoelectronic performances. To address these issues and to get insight into the essential physical properties of the 1D halide organic perovskites, we have integrated an electronically active organic cation, naphthalene diimide ammonium (NDIA), between the PbX 3 (X = I or Br) chains to form 1D quantum-well perovskite-like crystals (C 23 H 26 N 3 O 4 )Pb(I 1−n Br n ) 3 (0 < n < 1). Type-II band alignment is established between the electron-withdrawing NDIA bilayers and electron-donating inorganic PbX 3 sublattice, allowing efficient charge separation at the interface of the heterojunctions. In addition, the interfacial charge transport is further manipulated by halide engineering, where (C 23 H 26 N 3 O 4 )Pb(I 0.4 Br 0.6 ) 3 exhibits longer-lived charge carriers than that of the neat iodide or bromide counterparts. Combining the single crystal analysis with ultrafast spectral characterization, the prompt charge transfer and long-lived charge-separated state at the interface between the NDIA ligands and the mixed lead halide inorganic sublattices are deliberately elucidated. The presence of Br shortens the distance between the NDIA and halogen atoms to enhance the charge transition, meanwhile serving as an intermediate electronic state to manipulate the charge population to inhibit charge recombination, which greatly facilitates charge transportation. This work provides a prototype to manipulate the alignment of electronic levels between the perovskite sublattice and the organic spacer layer by halogen engineering to achieve desired charge carrier transport for a particular technological interest.