The present study is concerned with the structural and electronic properties of the low-index surfaces of the brookite form of titanium dioxide. A theoretical investigation is carried out using the density functional formalism under the nonlocal B3LYP approximation to calculate surface energies, band energy values, and to interpret the response to hydrostatic pressure of the bulk and surfaces of the brookite structure. In addition, phase transformations with pressure are predicted from the anatase and the rutile to the brookite polymorph at about 3.8 and 6.2 GPa, respectively. The orthorhombic structure and the fractional coordinates of brookite vary isotropically with the rise in pressure. The calculated band gap energy is 3.78 eV for the bulk brookite. The brookite surface stabilities follow the sequence (010) < (110) < (100), and the minimum gap energy value is found for the (110) surface.