Forward osmosis (FO) has received considerable interest for water- and energy-related applications in recent years. FO does not require an applied pressure and is believed to have a low fouling tendency. However, a major challenge in FO is the lack of high performance FO membranes. In the current work, novel nanofiltration (NF)-like FO membranes with good magnesium chloride retention were synthesized using layer-by-layer (LbL) assembly. The membrane substrate was tailored (high porosity, finger-like pores, thin cross-section, and high hydrophilicity) to achieve a small structural parameter of 0.5 mm. Increasing the number of polyelectrolyte layers improved the selectivity of the LbL membranes while reducing their water permeability. The more selective membrane 6#LbL (with 6 polyelectrolyte layers) had much lower reverse solute transport compared to 3#LbL and 1#LbL. Meanwhile, the FO water flux was found to be strongly affected by both membrane water permeability and solute reverse transport. Severe solute reverse transport was observed for the active-layer-facing-draw-solution membrane orientation, likely due to the suppression of Donnan exclusion as a result of the high ionic strength of the draw solution. In contrast, the active-layer-facing-feed-solution orientation showed remarkable FO performance (15, 20, and 28 L/m².h at 0.1, 0.5, and 1.0 M MgCl₂, respectively, for membrane 3#LbL using distilled water as feed solution), superior to other NF-like FO membranes reported in the literature. To the best of the knowledge of the authors, this is the first work on the synthesis and characterization of LbL based FO membranes.