The first direct evidence that Ti atoms are not equally distributed in the 12 crystallographically independent T sites of the MFI framework is presented on the basis of neutron diffraction data collected at the HRPD instrument of the ISIS pulsed neutron source. We found strong evidence indicating that T6, T7, and T11 are the most populated sites and weak evidence that Ti may be hosted in T10. Ti occupancy can be excluded for sites T1, T2, T4, T5, T9, and T12. The occupancy of the remaining sites is doubtful. Since defective silicalite has been shown to exhibit the same preferential sites (T6, T7, T11, and T10) for Si vacancies, it may be suggested that the incorporation mechanism of the Ti atoms in the MFI framework occurs via the insertion of titanium in the defective sites. This hypothesis implies that titanium has a mineralizing effect on the MFI framework, and it is supported by independent spectroscopic data on both TS-1 and defective silicalite. The results are discussed in comparison with the known substitution mechanisms in the T-sites of MFI-type structures.