An accurate knowledge of the Li i 4d-4f energy separation is essential for the determination of electric fields, as is pursued using several modern diagnostic techniques. However, there is a rather large spread in the values of this quantity in the available data sources. We have measured the Li i 4d-4f energy separation using a technique that combines laser-induced-fluorescence with the utilization of collisional excitations. The plasma used for these measurements is laser-produced, which allows for selection of an electron-density range for which line shifts due to the plasma microfields are sufficiently small. An observation of the forbidden 2p-4f line provides the information on the microfields that allows for accounting for the Stark-shifts and evaluating the 4d-4f energy separation in the field-free limit. A comparison of the measured value with a few previous measurements allows for resolving the uncertainties in this quantity.