Catalysis in microreactors allows reactions to be performed in a very small volume, reducing the environmental problems and greatly intensifying the processes through easy pressure control and the elimination of heat- and mass-transfer limitations. In this study, we report a novel method for the controlled synthesis of micrometre-thick mesoporous TiO2 catalytic coatings on the walls of long channels (>1 m) of capillary microreactors in a single deposition step. The method uses elevated temperature and introduces a convenient control parameter of the deposition rate (displacement speed controlled by a stepper motor), which allows deposition from concentrated and viscous sols without channel clogging. A capillary microreactor wall-coated with titania supported Bi-poisoned Pd catalyst was obtained using the method and used for the semihydrogenation of 2-methyl-3-butyn-2-ol providing 93 ± 1.5% alkene yield for 100 h without deactivation. Although the coating method was applied only for TiO2 deposition, it is nonetheless suitable for the deposition of volatile sols.