Through rigorous control of preparation conditions, organized monolayers with a highly reproducible structure can be formed by solution self-assembly of octaclecanethiol on GaAs (001) at ambient temperature. A combination of characterization probes reveal a structure with conformationally ordered alkyl chains tilted on average at 14 +/- 1 degrees from the surface normal with a 43 +/- 5 degrees twist, a highly oleophobic and hydrophobic ambient surface, and direct S-GaAs attachment. Analysis of the tilt angle and film thickness data shows a significant mismatch of the average adsorbate molecule spacings with the spacings of an intrinsic GaAs(001) surface lattice. The monolayers are stable up to similar to 100 degrees C and exhibit an overall thermal stability which is lower than that of the same monolayers on Au{111} surfaces. A two-step solution assembly process is observed: rapid adsorption of molecules over the first several hours to form disordered structures with molecules lying close to the substrate surface, followed by a slow densification and asymptotic approach to final ordering. This process, while similar to the assembly of alkanethiols on Au{111}, is nearly 2 orders of magnitude slower. Finally, despite differences in assembly rates and the thermal stability, exchange experiments with isotopically tagged molecules show that the octaclecanethiol on GaAs(001) monolayers undergo exchange with solute thiol molecules at roughly the same rate as the corresponding exchanges of the same monolayers on Au{111}.