The increasing role of catalysis by noble metals coupled with their high price requires the development of cheaper and more effective catalysts, e.g., highly dispersed supported catalyst. Herein, Pd supported on Al2O3 catalysts prepared by deposition-precipitation under different conditions were subjected to X-ray diffraction, N2-physisorption, NH3/CO2 temperature programmed desorption, CO-chemisorption, and field-emission transmission electron microscopy analyses, which revealed that the size and distribution of Pd particles were influenced by Al2O3 support type (particle size and phase transition) and preparation conditions (metal precursor type, pH value, and solution temperature). The Pd/Al2O3 catalysts were prepared using type A (particle size = 3 micron) or type B (particle size = 20 nm) as a support and PdCl2 (PC) or Pd(NO3)2·2H2O (PN) as a Pd precursor, respectively. In XRD results, type A (particle size = 3 micron) Al2O3 had γ and phase, and type B (particle size = 20 nm) Al2O3 had only thermally stable γ phase. In addition, Pd dispersion and crystallite size showed an obvious dependence on pH value, solution temperature and attractive/repulsive forces between the functional groups of Al2O3 and Pd precursors. Optimal results were obtained using PdCl2 (PC) as a Pd precursor and type B (particle size = 20 nm) as a support at 60 °C and pH 5.5.