The increasing demand for nanofiltration processes in drinking water treatment, industrial separation and wastewater treatment processes has highlighted several shortcomings of current state-of-the-art thin film composite (TFC NF) membranes, including limitations in chemical resistance, fouling resistance and selectivity. Polyelectrolyte multilayer (PEM) membranes provide a viable, industrially applicable alternative, providing significant improvements in these limitations. Laboratory experiments using artificial feedwaters have demonstrated selectivity an order of magnitude higher than polyamide NF, significantly higher fouling resistance and excellent chemical resistance (e.g., 200,000 ppmh chlorine resistance and stability over the 0-14 pH range). This review provides a brief overview of the various parameters that can be modified during the layer-by-layer procedure to determine and fine-tune the properties of the resulting NF membrane. The different parameters that can be adjusted during the layer-by-layer process are presented, which are used to optimize the properties of the resulting nanofiltration membrane. Substantial progress in PEM membrane development is presented, particularly selectivity improvements, of which the most promising route seems to be asymmetric PEM NF membranes, offering a breakthrough in active layer thickness and organic/salt selectivity: an average of 98% micropollutant rejection coupled with a NaCl rejection below 15%. Advantages for wastewater treatment are highlighted, including high selectivity, fouling resistance, chemical stability and a wide range of cleaning methods. Additionally, disadvantages of the current PEM NF membranes are also outlined; while these may impede their use in some industrial wastewater applications, they are largely not restrictive. The effect of realistic feeds (wastewaters and challenging surface waters) on PEM NF membrane performance is also presented: pilot studies conducted for up to 12 months show stable rejection values and no significant irreversible fouling. We close our review by identifying research areas where further studies are needed to facilitate the adoption of this notable technology.