AbstractNanoparticle networks can be synthesized by the self‐assembly of arrays of metal colloid particles linked by spacer molecules of different sizes. The particles are linked through reactive aluminum sites in a metal–organic shell around the metal particles. Rigid spacer molecules with functional groups at each end are used to bind at these reactive sites. The resulting networks have been characterized by various methods such as transmission electron microscopy (TEM), sorption analysis, X‐ray absorption spectroscopy (XAFS), anomalous small angle X‐ray scattering (ASAXS), metastable impact electron spectroscopy (MIES), and ultraviolet photoelectron spectroscopy (UPS). These investigations showed that the metal nanoparticles form aggregated networks with average distances between the metal particles that are determined by the sizes of the spacer molecules applied. In this way, porous as well as nonporous networks have been obtained. Whether accessible pores are formed depends on the type of spacer molecule. Furthermore, the properties of the metal particles have proved to be sensitive towards the reaction of the aluminum in the protective shells with the linker molecules. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)