The nanoparticles have been synthesized by sol-gel technique. X-ray diffraction, scanning electron microscopy, optical absorption spectroscopy, and electron paramagnetic resonance spectroscopy were used to characterize the sample. The X-ray diffraction results indicate the formation of nanocrystalline materials in tetragonal lattice with P42/nnm space group. The identical distribution of elements were confirmed by scanning electron microscopy with energy dispersive X-ray spectrometry and X-ray mapping. Electron paramagnetic resonance lineshapes of the samples are obtained at various (13 K, 77 K, and 300 K) temperatures. The isotropic lineshapes of the sample B1 are attributed to dipole-dipole interaction of Ti3+ ions. The incorporation of Al3+ ions into the sample B2–B5 the isotropic nature of the lineshapes are collapsed due to the distraction in crystal field. Optical absorption spectra results reveal the presence of Ag-TiO2 nanoparticles.