Hollow fibre RO membranes would be desired for many applications, but are notoriously difficult to fabricate. Here we demonstrate that combining layer-by-layer and interfacial polymerization (IP) allows straightforeward production of defect-free hollow fiber RO membranes. A polyelectrolyte multilayer (PEM) is used to fill the pores of a support membrane, to provide a controlled and smooth surface that can nevertheless act as an IP monomer reservoir. This approach is first demonstrated on a model surface, with IP layers being successfully applied on both poly(diallyldimethylammonium chloride) (PDADMAC)/poly(4-styrene sulfonate) (PSS) and poly(ethyl-eneimine) (PEI)/PSS PEMs. On plain hollow fiber support membranes, IP coating was found to have a success rate as low as 40%. However, by application of a PEM interlayer the success rate increases to 72% for PDAD-MAC/PSS and 90% for PEI/PSS. Also the separation performance of the successfully prepared IP membranes was significantly better when a PEM interlayer was applied, with higher NaCl retentions (from 94% to 97%), and better removal of organic micro-pollutants (from 96% to 98%), with just a small decrease in permeability (from 0.9 L/m(2)hbar to 0.7 L/m(2)hbar). Combining layer-by-layer and IP approaches can thus lead to the fabrication of defect free RO membranes with improved separation performance.