Interfacial self-assembly with the advantage of providing large-area, high-density plasmonic hot spots is conducive to achieving high sensitivity and stable surface-enhanced Raman scattering (SERS) sensing. However, rapid and simple assembly of highly repeatable large-scale multilayers with small nanoparticles remains a challenge. Here, we proposed a catassembly approach, where the "catassembly" means the increase in the rate and control of nanoparticle assembly dynamics. The catassembly approach was dropping heated Au sols onto oil chloroform (CHCl3), which triggers a rapid assembly of plasmonic multilayers within 15 s at the oil-water-air (O/W/A) interface. A mixture of heated sol and CHCl3 constructs a continuous liquid-air interfacial tension gradient; thus, the plasmonic multilayer film can form rapidly without adding functional ligands. Also, the dynamic assembly process of the three-phase catassembly ranging from cluster to interfacial film formation was observed through experimental characterization and COMSOL simulation. Importantly, the plasmonic multilayers of 10 nm Au NPs for SERS sensing demonstrated high sensitivity with the 1 nM level for crystal violet molecules and excellent stability with an RSD of about 10.0%, which is comparable to the detection level of 50 nm Au NPs with layer-by-layer assembly, as well as breaking the traditional and intrinsic understanding of small particles of plasmon properties. These plasmonic multilayers of 10 nm Au NPs through the three-phase catassembly method illustrate high SERS sensitivity and stability, paving the way for small-nanoparticle SERS sensing applications.