Abstract Multilayer particle assemblies that contained both Yb 2O 3 and SiO 2 particles were prepared on Si substrates by layer-by-layer self-assembly (LBLSA) as a new non-line-of-sight avenue of producing dense and uniform Yb 2O 3–SiO 2 coating microstructures. Morphological characteristics of the multilayer particle assemblies upon viscous sintering in the temperature range of 1300 to 1350 °C were evaluated in reference to those of multilayer assemblies that only contained SiO 2 or Yb 2SiO 5 particles. A 4-layer 0.5-μm SiO 2 particle assembly could be easily transformed to a dense and continuous coating structure after sintering. In contrast, a 4-layer 1.7-μm Yb 2SiO 5 particle assembly could not be consolidated and densified, as anticipated from the absence of the viscous sintering mechanism provided by the SiO 2 phase. Most of the coatings produced from sintering of Yb 2O 3–SiO 2 (0.5 μm) particles assemblies were dense and continuous with Yb 2Si 2O 7 and Yb 2SiO 5 as two predominant phases. The results suggest the feasibility of producing dense and uniform silicate coating structures by integrating the LBLSA concept with the viscous flow sintering mechanism provided by the SiO 2 particles.