One-pot deposition of Pd onto TiO2 has been achieved through directly contacting palladium(II) salt with nanosized functionalized TiO2 support initially obtained by 501-gel process using titanium isopropoxide and citric acid. Citrate groups act as functional moieties able to directly reduce the Pd salt avoiding any further reducing treatment. Various palladium salts (Na2PdCl4 and Pd(NH3)(4)Cl-2 center dot H2O center dot H2O) and titanium to citrate (Ti/CA) ratios (20, 50, and 100) were used in order to study the effect of the nature of the precursor and of the citrate content on the final Pd particle size and catalytic properties of the as-obtained Pd/TiO2 systems. Characterization was performed using N-2 adsorption-desorption isotherms, ICP-AES, FTIR, XRD, XPS, and TEM. The as-obtained hybrid Pd/TiO2 catalysts were tested in the selective hydrogenation (HYD) of an m,alpha beta-unsaturated aldehyde, i.e. cinnamaldehyde. Citrate-free Pd/TiO2-based catalysts present lower selectivity into saturated alcohol. However, citrate-functionalized Pd/TiO2 catalyst seems to control the selectivity, the particle size and dispersion of Pd NPs leading to high intrinsic activity. (C) 2011 Elsevier Inc. All rights reserved.