Liquid polymer nanocomposites (l-PNCs) have been prepared using silica nanoparticles with diameters of 15 nm (l-PNC-15) and 24 nm (l-PNC-24), and Jeffamine M-2070, an amine-terminated ethylene oxide/propylene oxide (PEO/PPO, ratio 31/10) copolymer. Jeffamine M-2070 was used as the host liquid in which the particles were suspended and was also grafted onto the particle surface to prevent aggregation. The grafting density of Jeffamine M-2070 on the particle surfaces was ∼0.75 chains nm(-2). When the total polymer content (surface layer + host) was greater than ∼30 wt %, the PNC was a liquid, while at lower polymer volume fractions the PNC was solid. In this work, the bulk and surface structures of l-PNCs with ∼70 wt % polymer and 30% silica are characterized and compared. Small-angle neutron scattering (SANS) was used to probe the bulk structure of the l-PNCs and revealed that the particles are well-dispersed with minor clustering in l-PNC-15 and substantial clustering in l-PNC-24. This is attributed to stronger van der Waals attractions between particles due to the larger particle size in l-PNC-24. Corresponding effects were revealed using tapping mode atomic force microscopy (TM-AFM) at the l-PNC-air interface; clustering was minimal on the surface of l-PNC-15 but significant for l-PNC-24 droplets. In regions of the l-PNC where the particles were well-dispersed, the spacing between particles is consistent with their volume fractions. This is the first time that the distribution of polymer and particles within l-PNCs has been imaged in situ.