This review analyzes the studies published, mainly in the last 10–15 years, on the synthesis, structure, and sensor properties of semiconductor nanocomposites. Particular attention is paid to the interaction between nanoparticles of the sensitive layer, and its effect on the structure, sensitivity, and selectivity of semiconductor sensor systems. Various mechanisms of interaction between nanoparticles in metal oxide composites are considered, including the incorporation of metal ions of one component into the structure of another, heterocontacts between different nanoparticles, and core–shell systems, as well as their influence on the characteristics of gas sensors. The experimental data and studies on the modeling of charge distribution in semiconductor nanoparticles, which determine the conductivity and sensor effect in one- and two-component systems, are also discussed. It is shown that the model which considers the interactions of nanoparticles best describes the experimental results. Some mechanisms of detection selectivity are considered in the conclusion.