Herein we describe the direct synthesis of lithium intercalated graphite by heating under vacuum or ball milling under pressurized Ar(g). Both methods allow for stoichometric control of Li-C ratio in battery-grade graphites and carbon fibers prior to formation of a solid electrolyte interphase. The products' surface chemistries, as probed by XPS, suggest that LiC6 are extremely reactive with trace amounts of moisture or oxygen. The open circuit potential and SEM data show that the reactivity of the lithiated battery-grade graphite and the carbon fiber can be related to the density of edge/defect sites on the surfaces. Preliminary results of spontaneous delithiation of Li-graphite in electrolyte are also given. (C) 2014 The Electrochemical Society. All rights reserved.