Almost all of a plant’s life activities involve electrochemical reactions. Plant electrical parameters respond quickly to environmental changes and are closely related to physiological activities. In this study, the theoretical intrinsic relationships between clamping force and leaf impedance (Z) or capacitive reactance (Xc) and capacitance (C) were revealed as 3-parameter exponential decay and linear models based on bioenergetics, respectively, for the first time. Leaf electrical characteristics including intrinsic impedance (IZ), capacitive reactance (IXc), capacitance (IC) and specific effective thickness (d) were successfully detected using the above-mentioned relationships and were used to manifest plant metabolic activity. The intracellular water-holding capacity (IWHC), water-use efficiency (IWUE), water-holding time (IWHT) and water transfer rate (WTR) of plant leaves were defined on the basis of IZ, IXc, IC and d, and applied to reflect the intracellular water metabolism. The results demonstrated that the leaves of Broussonetia papyrifera plants grown in agricultural soil had higher IC, d, IWHC, WTR, water content values and lower IZ, IXc values than those grown in moderately rocky desertified soil. The leaf IC, d, IWHC, WTR and water content values of herbaceous plants were higher than those of woody plants. Solanum tuberosum L. had higher leaf IC, d, IWHC and WTR values, but exhibited lower IZ, IXc, IWUE and IWHT values than Capsicum annuum L. This study highlighted that a plant’s electrical parameters based on bioenergetics clearly indicate its physiological process—e.g., the intracellular water metabolism.