The prime objective of this work is to demonstrate that chromium‐doped alumina fibers could, for the first time, be obtained via vapor liquid solid (VLS) deposition. Various procedures are described and discussed in the text. The mechanism for effective doping is also discussed, and the resulting fibers are analyzed. A modification of the basic VLS deposition process was investigated with the aim of producing doped α‐Al2O3 (α‐alumina or corundum) whiskers. Chromium‐doped (ruby) corundum whiskers were obtained by the introduction of Cr3+ in gas form within the argon flow used to attain inert furnace atmospheres. Various procedures are described and discussed in the text, using different chromium compounds, and the mechanism of effective doping is also discussed in each case.