Recent works on the electrochemical ion intercalation mechanisms in several HTObased host materials from organic electrolytes made some critical findings of general relevance. First, upon initial electrochemical reduction, more acidic structural protons of HTOs show a greater tendency to reduce and form hydrogen gas in the interlayer space. This is detrimental and needs to be addressed to improve the ICE and cycling stability of the HTO material. Second, it was reported that the Na + storage capacity can be increased in layered HTOs pillared with n-alkylamines that expand the interlayer spacing due to the availability of additional storage sites near alkyl groups. Third, our group recently suggested that functionalization of HTOs with n-alkylamine-based molecular pillars can improve the kinetics of the Li + intercalation reaction by triggering solvent cointercalation. All these findings motivated us to further investigate the molecular pillaring approach of HTO host materials with n-alkylamines as a versatile materials design strategy for titanate-based Na + intercalation anodes. We find that pillaring with n-propylamine results in improved Na + diffusion kinetics and electrochemical reversibility, higher Na + storage capacity, and improved ICE compared to the unmodified H2Ti4O9 host material. Moreover, electrochemical dilatometry measurements highlight the different volumetric response of the host materials dependent on the nanoconfinement properties of the HTO interlayer.