Ultrathin GaAs, AlGaAs and GaAs/InAs wire crystals (whiskers) as thin as 20-50 nm are grown by organometallic vapor phase epitaxy (OMVPE) using Au as a growth catalyst. It is found that the whisker shape and width can be controlled by adjusting the thickness of the Au deposited on the substrate surface and the substrate temperature duing OMVPE. A new technique employing a scanning tunneling microscope (STM) for controlling the whisker growth position on the substrate surface is described. Photoluminescence spectra from the GaAs whiskers show a blue shift of the luminescene peak energy as the whisker width decreases. The amount of blue shift energy is rather small compared to that calculated by a simple square potential well model. The discrepancy is explained by the cylindrical potential well model including the surface depletion effect. Atomic composition within the portion of 1-20 nm along the AlGaAs and GaAs/InAs whiskers has been analyzed by energy dispersive X-ray analysis in combination with transmission electron microscopy. This shows the exsitence of Au at the tip of the whisker and the composition change occurs over a length of less than 5 nm at the GaAs/InAs heterojunction.