Hollow ﬁber nanoﬁltration membranes can withstand much higher foulant concentrations than their spiral wound counterparts and can be used in water puriﬁcation without pretreatment. Still, the preparation of hollow ﬁber nanoﬁltration membranes is much less established. In this work, we demonstrate the design of a hollow ﬁber nanoﬁltration membrane with excellent rejection properties by alternatively coating a porous ultraﬁltration membrane with a polycation, a polyzwitterion, and a polyanion. On model surfaces, we show, for the ﬁrst time, that the polyzwitterion poly N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylam-monium betaine (PSBMA) can be incorporated into traditional polyelectrolyte multilayers based on poly(styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC). Furthermore, work on model surfaces allows a good characterization of, and insight into, the layer build-up and helps to establish the ptimal membrane coating conditions. Membranes coated with these multilayers have high salt rejection of up to 42% NaCl, 72% CaCl2, and 98% Na2SO4 with permeabilities of 3.7−4.5 l·m−2·h−1·bar−1. In addition to the salt rejections, the rejection of six distinctively diﬀerent micropollutants, with molecular weights between 215 and 362 g·mol−1, was investigated. Depending on the terminating layer, the incorporation of the polyzwitterion in the multilayer results in nanoﬁltration membranes that show excellent retentions for both positively and negatively charged micropollutants, a behavior that is attributed to dielectric exclusion of the solutes. Our approach of combining model surfaces with membrane performance measurements provides unique insights into the properties of polyzwitterion-containing multilayers and their applications.