We apply neutron reflectivity to probe the internal structure of spin-assisted layer-by-layer (SA-LbL) films composed of electrostatically assembled polyelectrolytes. We find that the level of stratification and the degree of layer intermixing can be controlled by varying the type and concentration of salt during SA-LbL assembly. We observe well-defined layer structure in SA-LbL films when deposited from salt-free solutions. These films feature 2-nm-thick bilayers, which are ∼3-fold thicker than those in conventional LbL films assembled under similar conditions. The addition of a 10 mM phosphate buffer promotes progressive layer interdiffusion with increasing distance from the substrate. However, adding 0.1 M NaCl to the phosphate buffer solution restores the layer stratification. We also find that SA-LbL films obtained from buffer solutions are more stratified as compared to the highly intermixed layers seen in conventional LbL films from buffer. Our results yield new insights into the mechanism of SA-LbL assembly and the final micro structure in comparison with traditional LbL assemblies © 2009 American Chemical Society.