This work is devoted to the study of the magnetic properties and Electron Paramagnetic Resonance (EPR) spectroscopy of TiO2:Fe nanoparticles doped with Al in different structural states. The sol-gel methods have been used to obtain the particles in both crystalline (average size from 3 to 20 nm) and X-ray amorphous states. The electron paramagnetic resonance spectra of crystalline samples TiO2:Fe doped with aluminum besides a resonance line with g-factor ~2 exhibit a small signal with a g-factor of 4.3 from Fe3+ ions with rhombohedral distortions. The fraction of Fe3+ with rhombohedral distortions increases with increasing aluminum content. For the amorphous state at Al doping, the resonance with a g-factor of 4.3 is completely dominant in the electron paramagnetic resonance spectrum. The density functional theory calculation shows that aluminum prefers to be localized near iron ions, distorting the nearest Fe3+ environment. The complex integral electron paramagnetic resonance spectrum of all samples was fitted with sufficient accuracy by three separate resonance lines with different widths and intensities. The temperature behavior of the electron paramagnetic resonance spectrum can be described by the coexistence of paramagnetic centers (isolated Fe3+ ions including dipole-dipole interactions) and iron clusters with negative exchange interactions.