Laser ablation is well established as a tool for surface processing. Various types of materials ranging from polymers to inorganic crystals and metals have been extensively studied. Laser-induced ablation of solid surface makes an accurate vaporization of the surface possible, and most of the species in the ablation plume are in the atomic state. We have developed an extremely sensitive atomic detection method called LAAF (Laser Ablation Atomic Fluorescence) spectroscopy. In LAAF spectroscopy, the ablation was used to atomize the sample surface, and atoms in the ablation plume were detected by laser-induced fluorescence (LIF) spectroscopy. In the detection of Na atoms in pure water, we had acquired the limit of detection such as 0.6 fg for signal-to-noise ratio (SIN) as unity. This LAAF spectroscopy is one of the most sensitive techniques in trace element analysis, and is presently applied to solid surface analysis. In the work, LAAF spectroscopy is applied for nanometer solid surface analysis of Na-doped poly-methylmethacrylate (PMMA). The analysis is also extended to silicon and different metals.