Self-assembly (SA) of long-chain alkanethiols on copper was studied. Two factors were found to have substantial influence on the SA process : (i) the chemical reactivity of Cu toward substances present in the adsorption solution, particularly the solvent, and (ii) surface pretreatment, which influences the amount of oxide and the surface morphology. Both factors are less important in the case of SA onto gold because of its chemical inertness. Monolayers of octadecanethiol (C18SH) were adsorbed from different solvents (ethanol, toluene, and bicyclohexyl) at various thiol concentrations onto Cu surfaces pretreated in several different ways. The monolayers were characterized by contact-angle measurements, grazing-incidence Fourier transform infrared spectroscopy, and scanning force microscopy. Ethanol, the most common solvent for alkanethiol SA, is found to have a negative effect on monolayer SA apparently because of its chemical reactivity toward copper. With toluene as a solvent, better oriented and more crystalline monolayers are obtained provided that a higher thiol concentration is used to compensate for the higher solubility of thiols in toluene. Treatment of the Cu surface prior to SA is shown to significantly improve the SA by reducing the amount of surface oxide and the surface corrugation. The effect of the solvent is more critical than surface oxidation; hence, high-quality monolayers are formed in the presence of thin oxide layers on Cu surfaces. Superior C18SH monolayers, in terms of organization and crystallinity, are obtained by SA from toluene onto Cu surfaces sputtered-annealed in high vacuum, even when the Cu surface is subjected to short exposure to air before SA.