In this study, we introduce a layer-by-layer (LbL) assembly method to prepare a reverse osmosis (RO) desalination membrane that consists of a hybrid combination of [polyelectrolyte (PE)/montmorillonite (MTM)]_n layers. First, adopting poly(allylamine hydrochloride) (PAH) for a PE layer, an RO test showed that the permeate flux of water through (PAH/MTM)_n multilayer-coated membranes decreased from ∼25.5 to ∼8.3 L·m⁻²·h⁻¹ with the increased bilayer number from n=9 to n=18. At the same time, the corresponding ion rejection with respect to NaCl is increased from ∼30 to ∼81%. Despite the increased ion rejection performance, (PAH/MTM)_n membranes exhibit a poor chlorine resistance, as frequently observed in commercial polyamide-based RO membranes. In our previous study, it was noted that the RO membranes, prepared just from the PE multilayers (i.e., [PAH/poly(acrylic acid) (PAA)]_n layers), showed a marked chlorine tolerance, but concomitantly very low permeate flux (∼4–5 L·m⁻²·h⁻¹). Considering the significant drawback in each case (poor chlorine tolerance for (PAH/MTM)_n layers and low permeate flux for (PAH/PAA)_n layers), we proposed to combine the layer constituents primarily by inserting PAH/PAA layers between two adjacent PAH/MTM layers. Indeed, the flux is maintained at ∼7.5±0.5 L·m⁻²·h⁻¹, comparable to commercial membranes, while the salt rejection ability is as high as ∼75±2.5% and the stability against the chlorine attack is well preserved with ∼74±5.0% ion rejection after the NaOCl treatment.