As titanium oxide is a well-known photocatalyst, we investigated the effects of silver content and nanostructural morphology on the photocatalytic degradation of two dyes, methylene blue and rhodamine B. Two nano-formulations were utilized, including nanofibers and nanoparticles. Silver-grafted titanium oxide nanofibers were synthesized using the electrospinning of silver nitrate/titanium isopropoxide/poly(vinyl acetate) sol-gel. The nanoparticulate form was obtained by calcination of a ground powder prepared from the same electrospun sol-gel. The results affirmed the advantage of the silver-grafted titanium oxide nanostructures over the silver-free ones. Increasing the silver content in the nanofibers led to increases in their surface area, which is an important parameter in heterogeneous catalytic chemical reactions. Therefore, the results strongly suggest the use of silver-grafted titanium oxide in a nanofibrous form. These results further support utilizing Ag-loaded titanium oxide nanofibers as a photocatalyst.