Metal (nano)clusters attract a lot of attention due to their size-dependent optical, electrical and chemical properties. They can be further modified by creating cluster assemblies as well as their ultrathin films. This thesis discusses the formation of such films using Langmuir-Blodgett technique, whereby the cluster particles are compressed on a water surface using surface pressure as a feedback mechanism, followed by their deposition on solid surfaces via a vertical extraction of a substrate. The principles guiding the particle organization in Langmuir and Langmuir-Blodgett films of gold and silver nanoparticles are reviewed in more detail, whereby factors such as particle size, ligand composition, solvent or solution concentration are considered. Langmuir-Blodgett films of Au₃₈(SC₂H₄Ph)₂₄ cluster transferred onto mica or silicon in the bi-/trilayer regime are then analyzed using atomic force microscopy (AFM) and X-Ray reflectivity (XRR) to probe their morphology and vertical organization respectively on the mesoscale. With the use of fast AFM and Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) the hexogonally close-packed arrangement as well as the correlation on the nanoscale are investigated. Bimodal AFM is also used to quantify the nanomechanical properties of the film. Together the techniques have demonstrated that the films are most stable and best organized in the form of trilayers, whereby, crucially for applications, they can form highly extended ordered films. Finally, the properties of Au₂₅(SC₂H₄Ph)₁₈ cluster are altered by linking the monomers into oligomers using a chiral bidentate ligand, diBINAS. The small assemblies are characterized in solution using primarily small-angle X-ray scattering (SAXS) to determine the structural properties of the oligomers. This data is supported by a range of spectroscopic techniques (UV-Vis, fluorescence, circular dichroism) as well as other techniques that help determine the size and/or the structure such as diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY NMR), transmission electron microscopy (TEM) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI TOF-MS), electron paramagnetic resonance (EPR) and finally density functional theorem (DFT) calculations. Crucially, it was demonstrated that by using a bidentate ligand the post-separation dynamism of the system is drastically reduced, allowing for very high monodispersity of the oligomers. When combined, the Langmuir-Blogett film deposition as well as oligomerization reactions have demonstrated that the novel properties of metal clusters can be further fine-tuned and/or enhanced through collective action in 2D and linear assemblies.