<div><p>Seven new 4-hydroxybenzyl-substituted glutathione derivatives (<b>2</b>–<b>8</b>), together with a known analogue (<b>1</b>), were isolated from the aqueous extract of <i>Gastrodia elata</i> Blume rhizomes. Their structures were determined by using spectroscopic and chemical methods. The absolute configurations of <b>1</b>–<b>8</b> were assigned by using Marfey's method, combined with comparing the NMR and CD spectroscopic data of sulfoxide moieties in <b>3</b>–<b>6</b> with those of <i>S</i>-(4-hydroxybenzyl)cysteine sulfoxide stereoisomers (<b>9</b>–<b>12</b>) synthesized as authentic samples. The configurations of <b>9</b>–<b>12</b> were confirmed by electronic CD calculations based on the quantum-mechanical time-dependent density functional theory. Furthermore, the structures of <b>1</b>, <b>3</b>, <b>5</b>, <b>7</b>, and <b>8</b> were verified by synthesis. Compound <b>3</b> was active against serum deprivation-induced PC12 cell damage and synthetic <b>9</b>–<b>14</b> exhibited activity against Fe<sup>2+</sup>-cysteine induced rat liver microsomal lipid peroxidation.</p></div
