We propose a new scheme of matrix-free laser desorption/ionization with cation assistance for surface mass spectrometry of self-assembled monolayers (SAMs) of alkanethiolates on gold substrates and gold nanoparticles (NPs). In a proof-of-concept experiment, a simple treatment using an aqueous salt solution such as NaI(aq) was shown to lead to a significant laser desorption/ionization, producing the characteristic (disulfide) ions of alkanethiolate molecules from the monolayers. Further efforts to understand the mechanism were also given, including laser power and salt concentration dependence studies. In the power dependence study, the characteristic ions were found to be produced at low laser power where no gold substrate species was seen. At high laser power, the generation of gold species, Au(+)-Au5(+), resulted in a saturation behavior in the characteristic mass peak for alkanethiolate molecules. In addition, characteristic ions with gold adducts were not observed at any laser power. With increasing salt concentration, the characteristic mass peak was gradually increased. The results suggest that the adduct formation of a cation with alkanethiolates in the monolayers provide a facile pathway to supply a charge to UV laser-desorbed secondary neutrals for mass spectrometric detection. This cation-assisted laser desorption/ionization (CALDI) mass spectrometry was further examined with the SAMs and mixed SAMs with various terminals such as -OH, -OCH3, -NH2, -ethylene (-CH=CH2), and -acetylene (-C[triple bond]CH). The CALDI method was also successfully applied to surface mass spectrometry of monolayer-protected gold NPs (approximately 16 nm diameter) with OH- and COOH-terminated SAMs. The unique advantages of the matrix-free CALDI method may extend our capability in investigations of interfacial chemistry at SAMs as well as mass spectrometric applications using biochips and nanoparticles.