Characterizing the structure and dynamic properties of a single monolayer is a challenge due to the minute amount of material that is probed. Here, EPR spectroscopy is used for investigating the spatial and temporal organization of self-assembled monolayers of 5- and 16-doxyl stearic acid (5 DSA and 16 DSA, respectively) adsorbed on a GaAs substrate. The results are complemented with FTIR and ellipsometery measurements, which provide the evidence for the formation of monolayers. Moreover, a comparison with the FTIR spectrum of a monolayer of stearic acid shows that the monolayers of the spin labeled molecules are less packed due to the hindrance introduced by the labeling group. The EPR spectra provide a new insight on the ordering in the layer and more interestingly, it reveals the time dependence of the organization. For 5DSA, with the spin-label group situated close to the substrate, the EPR spectrum immediately after adsorption is poorly resolved and dominated by the spin-exchange interaction between neighboring molecules. As time increases (up to 1 week) the resolution of the 14N hyperfine coupling increases, revealing a better organized monolayer where the molecules are more homogenously spaced. Moreover, the spectrum of the layer, after reaching equilibrium, shows that there is no motional freedom near the GaAs surface. Orientation dependence measurements on the equilibrated sample show the presence of a preferred orientation of the molecules, although with a wide distribution. The spectrum of the 16DSA monolayer, where the nitroxide spin label is situated at the end of the chain, far from the surface, also showed a poorly resolved spectrum at short times, but unlike 5DSA, it did not exhibit any time dependence. Through EPR line-shape simulations and by comparison with FTIR results, the differences between 5DSA and 16DSA were attributed to difference in coverage caused by the bulky spin label near the surface in the case of 5DSA.