Photoresist and electron beam lithography techniques were used to fabricate embedded Ag bowtie and diabolo nanostructures with various apex angles on the surface of a TiO2 film. The reinforced localized surface plasmon resonance (LSPR) and electric field generated at both the Ag/TiO2 and air/TiO2 interfaces enabled high light absorbance in the TiO2 nanostructure. Results for both the bowtie and diabolo nanostructures showed that a reduction in the apex angle enhances both LSPR and Raman intensity. The maximum electric current density observed at the apex indicates that the strongest SPR confines at the tip gap of the bowtie and corners of the diabolo. In a long-wavelength region, as the apex angle increases, the resonant peak wavelength of the standing wave matches the increased length of the prism edges of the bowtie and diabolo to create a redshift. In a short-wavelength region, as the apex angle increases, the blueshift of the resonant peak wavelength is presumably attributable to the increase in the effective index of the local surface plasmon polariton standing wave mainly residing along both the bowtie and diabolo axes. The redshift and blueshift trend in the simulation results for the resonant peak wavelength agrees well with the experimental results. The fastest photocatalytic rate was obtained by placing the Ag/TiO2 bowtie at an apex angle of 30° in the methylene blue solution, revealing that the plasmonic photocatalysis causes the highest degradation efficiency. This is because the Schottky junction and LSPR can stimulate many valid radicals for the environmental improvement.