The present paper reports the fabrication of novel types of hybrid fibrous photocatalysts by combining block copolymer (BCP) templating, sol–gel processing, and coaxial electrospinning techniques. Coaxial electrospinning produces core–shell nanofibers (NFs), which are converted into hollow porous TiO₂ NFs using an oxidative calcination step. Hybrid BCP micelles comprising a single plasmonic nanoparticle (NP) in their core and thereof derived silica-coated core–shell particles are utilized as precursors to generate yolk-shell type particulate inclusions in photocatalytically active NFs. The catalytic and photocatalytic activity of calcined NFs comprising different types of yolk-shell particles is systematically investigated and compared. Interestingly, calcined NFs comprising silica-coated yolk-shells demonstrate enhanced catalytic and photocatalytic performance despite the presence of silica shell separating plasmonic NP from the TiO₂ matrix. Electromagnetic simulations indicate that this enhancement is caused by a localized surface plasmon resonance and a confinement effect in silica-coated yolk-shells embedded in porous TiO₂ NFs. Utilization of the coaxially electrospun TiO₂ NFs in combination with yolk-shells comprising plasmonic NPs reveals to be a potent method for the photocatalytic decomposition of numerous pollutants. It is worth noting that this study stands as the first occurrence of combining yolk-shells (Au@void@SiO₂) with porous electrospun NFs (TiO₂) for photocatalytic purposes and gaining an understanding of plasmon and confinement effects for photocatalytic performance. This approach represents a promising route for fabricating highly active and up-scalable fibrous photocatalytic systems.