The present paper constitutes the first stage of a systematic study of the influence of precursor nature and structure on the catalyst behavior in dehydrogenation of propane, by varying the nature of the ligands and the nuclearity of the starting compounds at fixed net surface potentials. We show results obtained by the use of different Cr carboxylates to design the Cr2O3/gamma-Al2O3 catalyst at low loadings and these results are compared with those obtained for chromic acid. The following short chain chromium compounds were selected as precursors: citrate (Cr(In)), dimer monohydrate acetate (Cr(II)), acetyl acetonate (Cr(III)) and hydroxyacetate (Cr(III)). An exhaustive characterization by means of BET surface, XPS, XRD, X-ray fluorescence, laser Raman spectroscopy, EPR and catalytic test in propane dehydrogenation enabled us to draw relevant conclusions. Low metal-support interaction might be the major cause of polymerization in Carbox. The interaction between the chromia phase and the support surface, which stabilizes different oxidation stages and coordinations of the chromia species, defines the surface architecture. Part of the Cr3+ is, incorporated in the vacant octahedral sites of the spinel surface. The larger extension of this phenomenon in Cral might be responsible for surface inactive species that could cause a loss of catalytic activity. Deactivation between cycles might depend on the catalyst stabilization by the incorporation of Cr3+ into the support structure. The surface array of monomer species in a polymer species environment stabilizes the catalyst architecture and confers characteristics of high stability between cycles. The above considerations permit to infer that chromium carboxylates are interesting precursors for the control of surface species in chromia/Al2O3 catalysts.