Layer-by-layer assembly of gold nanoparticle/dendrimer composite films is described in this article. Crosslinking the nanoparticles through disulfide-functionalized polyphenylene dendrimers enables well-controlled film deposition and serves to mechanically reinforce the film material. Chemiresistors based on such films (see Figure) display short response times, high sensitivity to volatile organic compounds, and a desirable low sensitivity to humidity.