The incorporation of various nanofillers into the interfacial polymerization (IP) process is widely applied to prepare higher performance NF membranes. However, few studies have reported the influence of nanofillers on nanocomposite membrane formation in the IP process. Here, an optical microscope was employed to study the change rule in the 8-NH2-POSS/PSA nanocomposite membrane formation process due to the addition of 8-NH2-POSS nanoparticles. First, the addition of 8-NH2-POSS reduced the diffusion rate of the polyacrylamide hydrochloride (PAH) water phase on the surface against the oil phase because of the interaction with the PAH molecules. Furthermore, the 8-NH2-POSS/PSA nanocomposite membrane structure was more homogeneous and exhibited uniform pinhole defects distribution due to the interaction of the 8-NH2-POSS nanoparticles to the PAH segment. A significant separation performance was observed in the 8-NH2-POSS/PSA nanocomposite membrane due to the hydrophilicity and positive charge of the 8-NH2-POSS nanoparticles. The permeation flux and MgCl2 rejection of the 8-NH2-POSS/PSA nanocomposite membrane increased up to 50.5 L/m2 h at 0.5MPa and 94.8%, respectively, which corresponded to increases of 73.5% and 8.7% as compared to the pristine PSA membrane. 8-NH2-POSS/PSA nanocomposite membranes have great application potential in the water softening and treatment of divalent metals ions under acidic conditions.