In this work, we investigate the layered titanate H2Ti4O9•H2O and increase its interlayer spacing from 0.88 to 1.58 nm by insertion of organic molecular pillars. This allows in a first step to study the influence of nanoconfinement geometry on the electrochemical ion intercalation properties. Furthermore, using either propylamine (PA) or 1,6-hexanediamine (HDA) pillars, an identical expanded interlayer spacing is obtained. But while HDA pillars with two ammonium groups cross-link the titanate layers, PA pillars are non-cross-linking, likely impacting how electrochemically-induced strain is compensated within the host lattice. We utilize a combination of experimental and theoretical methods to derive precise structural models of the pillared titanates. Electrochemical Li + intercalation capacity from organic electrolyte can be increased from ca. 2.1 to 2.95 Li + per tetratitanate when pillaring with noncross-linking PA molecules. Using a combination of operando X-ray diffraction (XRD), electrochemical dilatometry (ECD) and electrochemical quartz crystal microbalance (EQCM), we unambiguously identify a nanoconfinement-induced change in intercalation mechanism from solid-solution intercalation to ion-solvent cointercalation.