Yolk-shell nanostructured photocatalyst which consists of inner core photocatalytic particles and outer silica shell exhibits high photocatalytic efficiency and molecular size selectivity due to the molecular sieving property of the outer shell. Creation of extended porosity in the shell endows it with improved adsorption properties and size selectivity toward targeted reactants. In this study, yolk shell nanostructured photocatalyst consisting of TiO2 NPs core and porous silica shell with controllable pore size was fabricated through a facile single-step dual-templating approach utilizing oil-in-water (O/W) micro emulsions and amphiphilic protein molecules. Addition of optimum amount of protein (ovalbumin) as a sacrificial template together with O/W microemulsion during the synthesis led to the expansion of average pore size from 2.0 to 3.6 nm, while retaining TiO2-encapsulated yolk-shell nanostructures. Photocatalytic degradation tests using gaseous 2-propanol and huge proteins as model substrates clearly revealed that the obtained material (TiO2@HSS_pro) showed superior photocatalytic performances with both improved photocatalytic efficiency and molecular size selectivity due to the increased surface area and expanded pore diameter.