A series of hydrogen titanates was synthesized that exhibits variations in (i) interlayer spacing from 0.88 to 1.58 nm and (ii) in the electrochemo-mechanical properties of the interlayer space. The variations are based on the insertion of organic pillar molecules into HTO to expand the nanoconfined interlayer space, and by comparing non-cross-linking monoamine pillars (HTO-PA) with cross-linking diamine pillars (HTO-HDA). Using spectroscopic, thermogravimetric, transmission electron microscopy and diffraction experiments in combination with density functional theory, we propose optimized atomistic structural configurations of the pillared HTO materials that show consistent interlayer spacings.