In this study, a surfactant assisted hydrometallurgical procedure was proposed for preparation of hierarchically mesoporous nanoparticles of titanium dioxide (TiO 2 ) from ilmenite concentrate. A hydrometallurgical procedure was developed in order to prepare titanium solution (Ti-sol) in an alkaline solution of NH 3 or NaOH in assistance of H 2 O 2 as oxidizing agent. Afterwards, the prepared Ti-sol was used as titanium source for preparation of a hierarchically mesoporous structure of TiO 2 in assistance of hexadecyltrimethyl ammonium bromide (HDTMA-Br) as structure directing agent. Different techniques were used to characterize the hierarchically mesoporous TiO 2 structures such as XRD, SEM, and BET. When Ti-sol was prepared in NaOH media mesoporous structure of small mesopores ( 3 nm) were created by hydrolysis of titanium (Na x Ti(O 2 ) y (OH) j ) to the HDTMA micelles through an electrostatic interaction of TiOH + -Br - -HDTMA + . During this reaction small mesoporous clusters of titanium oxide were created and coagulated with the help of micelles to form nanoparticles. Upon calcination two types of pore were created small ( 3 nm) and large ( 15 nm) mesopores. A large mesoporous nanoparticles were formed when Ti-sol was prepared in NH 3 which resulted in lack of strong electrostatic interaction between HDTMA micelles and hydrolyzed titanium ((NH 4 ) 2 TiO 6 ). In this conditions small clusters of hydrolyzed titanium were furthers coagulated by micelles through a weak hydrophilic interaction which resulted in large mesopores upon calcination. This study provides information about preparation of hierarchically mesoporous titanium dioxide with small nanoparticle sizes from naturally available sources with high grade of purity suitable for variety of applications such as photocatalysts and solar cells.