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Palladium catalysts supported by a mesoporous form of sulfonated poly-divinylbenzene, Pd/&micro, S-pDVB10 (1%, w/w) and Pd/&micro, S-pDVB35 (3.6% w/w), were applied to the direct synthesis of hydrogen peroxide from dihydrogen and dioxygen. The reaction was carried for 4 h out in a semibatch reactor with continuous feed of the gas mixture (H2/O2 = 1/24, v/v, total flow rate 25 mL&middot, min&minus, 1), at 25 &deg, C and 101 kPa. The catalytic performances were compared with those of a commercial egg-shell Pd/C catalyst (1%, w/w) and of a palladium catalyst supported by a macroreticular sulfonated ion-exchange resin, Pd/mS-pSDVB10 (1%, w/w). Pd/&micro, S-pDVB10 and Pd/C showed the highest specific activity (H2 consumption rate of about 75&ndash, 80 h&minus, 1), but the resin supported catalyst was much more selective (ca 50% with no promoters). The nanoparticles (NP) size was somewhat larger in Pd/&micro, S-pDVB10, showing that either the reaction was structure insensitive or diffusion limited to some extent over Pd/C, in which the support is microporous. The open pore structure of Pd/&micro, S-pDVB10, possibly ensuring the fast removal of H2O2 from the catalyst, could also be the cause of the relatively high selectivity of this catalyst. In summary, Pd/&micro, S-pDVB10 was the most productive catalyst, forming ca 375 molH2O2&middot, kgPd&minus, 1&middot, h&minus, 1, also because it retained a constant selectivity, while the other ones underwent a more or less pronounced loss of selectivity after 80&ndash, 90 min. Ageing experiments showed that for a palladium catalyst supported on sulfonated mesoporous poly-divinylbenzene storage under oxidative conditions implied some deactivation, but a lower drop in the selectivity, regeneration upon a reductive treatment or storage under strictly anaerobic conditions (dry-box) lead to an increase of the activity but to both a lower initial selectivity and a higher drop of selectivity with time.