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Molybdenum disulfide is a promising candidate for various applications in electronics, optoelectronics, or alkali-ion batteries. The natural presence of the van der Waals gap allows intercalating alkali ions, such as lithium, into MoS2 films. Intercalation can modify the electronic structure as well as the electrical and optical properties. Here, we present a structural, optical, and electrical characterization of Li-intercalated few-layer MoS2 films. The intercalation was carried out by annealing MoS2 film in the presence of Li2S powder, serving as a lithium source. The initial MoS2 layers were prepared by pulsed laser deposition (PLD) and by sulfurization of 1 nm thick Mo film (TAC). The presence of lithium was confirmed by synchrotron-based x-ray Photoelectron Spectroscopy. The Raman spectroscopy, x-ray diffraction, and optical absorption measurements confirmed semiconducting behavior for all samples. All samples exhibited the thermally activated dependence of the electrical resistance, R, typical for the Efros–Shklovskii variable range hopping in a disordered semiconductor, ln R(T) ∝ (TES/T)1/2, where kBTES is the hopping activation energy. The PLD-grown MoS2 samples exhibited a relatively mild initial disorder primarily caused by grain boundaries. Lithium intercalation led to an increase in disorder, evident in the increase in kBTES and a substantial rise in electrical resistance. The TAC-grown undoped MoS2 sample already exhibited significant resistance, and the impact of Li intercalation on resistance was minimal. This observation was attributed to the fact that the TAC-grown MoS2 samples exhibit a perturbed stoichiometry (the S:Mo ratio ∼ 2.20), causing strong disorder even before Li intercalation. The electron doping caused by lithium, if any, was completely obscured by the effect of disorder. [ABSTRACT FROM AUTHOR]