Lithium chloride was added to systematically alter the phase separation behavior, and hence, the nature of urea phase connectivity, in a series of plaques based on molded flexible polyurethane foam formulations. The plaques prepared were found to possess varied levels of urea phase connectivity that was examined at different length scales using several characterization techniques. SAXS, TEM, and t-AFM were used to show that addition of LiCl systematically reduced the formation of the urea aggregate structures typically observed in flexible polyurethane foam formulations and thus led to a loss in urea phase connectivity at the macrolevel, SAXS, DSC, and DMA revealed that formulations with and without LiCl exhibited similar interdomain spacings and soft segment glass transitions, suggesting that incorporation of LiCl did not prevent the plaques from undergoing partial microphase separation. WAXS demonstrated that addition of LiCl led to a loss in the local ordering of the hard segments within the microdomains, i.e., it led to a reduction of microlevel connectivity or the regularity in segmental packing of the urea phase. High-magnification t-AFM images showed that increasing the LiCl content dispersed the urea component more homogeneously and in a more uniform manner in the polyol matrix, and thus altered the connectivity of the urea phase at the microdomain level.