Conductivity and open circuit potentials of lithium solvated electron solutions (Li SESs) based on triphenylene (TRI) in tetrahydrofuran (THF) were studied. It was found that those solutions with Li:TRI ratio >0.5 demonstrate much higher conductivity comparing to naphthalene based Li SES of same concentration, which can be related to TRI π-stacking properties. Based on the values of open circuit voltage in a half-cell, the values of entropy and enthalpy change were calculated for the Li:TRI ratios of 2:1 and 4:1. The value of ΔS for Li4.0 (TRI) (THF)123 is higher than the one for naphthalene based Li SES with Li:PAH ratio = 1:1. The obtained values are much higher than those for solid state electrodes used in lithium ion batteries. Based on quantum chemical modeling of lithium-triphenylene interactions, it was shown that the unusually high values of conductivity could be related to the formation of a dimeric conductive complex.