Catalysts TS-1, TS-2 (each hydrophobic) and Ti-BETA (hydrophilic) prepared by reported methods to contain Ti 0.40, 0.49, and 0.57% (as TiO2), resp., were used, 1%, in the hydroxylation of PhOH (13 h, 70degreesC) with 30% H2O2 added at 1:1, 3:1, or 5:1 mole ratio in MeOH or EtOH, 30%, as medium. In MeOH and at the 1:1 ratio, 1,2- and 1,4- (but not 1,3-)benzene diols were formed in max. yields of 3.7, 6.6, 6.7, 8.7 (max. selectivities of 43.7 and 56.3 mol %); and 2.9,7.3 mol% to with max. PhOH conversions of 10.3, 15.4 and 10.2 mot % over the resp. catalysts. TS-2 was most active; its crystals were identified (SEM) as prisms, about 2x0.5-mum in size. To make the 1,4-isomer prevail over the 1,2-, the 3:1 reactant ratio is advisable. In EtOH, the hydroxylation was less selective and 1,3-benzenediol was formed.