A capillary condensation process was developed for the purpose of forming interconnections between nanoparticles at low temperatures. The process was performed in a temperature-controlled flow chamber on nanoparticle agglomerates deposited at submonolayer coverage on a transmission electron microscope grid. The partial pressure of the condensing species, tetraethyl orthosilicate, and the temperature of the chamber were adjusted in order to obtain the various saturation conditions for capillary condensation. The modified samples were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, BET surface area method, and scanning transmission electron microscopy with electron energy-loss spectrometry. Experimental results show that bridge-shaped layers were dominantly formed in the neck region between particles and were composed of amorphous silica. The analysis of TEM micrographs verified that the coverage of the layers is strongly dependent on the saturation ratio. Image analysis of TEM micrographs shows that this dependency is qualitatively in agreement with theoretical predictions based on the classical Kelvin equation for the specific geometries in our system.