Lewis acid base adducts between SF4 and the oxygen bases tetrahydrofuran, cyclopentanone, and 1,2-dimethoxyethane were synthesized and characterized by Raman spectroscopy and X-ray crystallography. Crystal structures of (SF4 center dot OC4H8)(2), SF4 (OC4H8)(2), SF4 center dot CH3OC2H4OCH3, and SF4 center dot(O=C5H8)(2) show weak S center dot center dot center dot O chalcogen bonding interactions ranging from 2.662(2) to 2.8692(9) angstrom. Caffeine, which has three Lewis basic sites, was reacted with SF4 and one aliquot of HF forming C8H10N4O2 center dot 2SF(4)HF, which was also characterized by X-ray crystallography. Density functional theory calculations aided in the assignment of the vibrational spectra of (SF4 center dot OC4H8)(2), SF4 center dot(OC4H8)(2), SF4 center dot CH3OC2H4OCH3, and SF4 center dot(O=C5H8),. Bonding was studied by natural bond order and the quantum theory of atoms in molecules analyses.