Lithium salts have been shown to dramatically increase the conductivity in a broad range of polymeric and small molecule organic semiconductors (OSs). Here we demonstrate and identify the mechanism by which Li(+) p-dopes OSs in the presence of oxygen. After we established the lithium doping mechanism, we re-evaluate the role of lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI) in 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-Spirobifluorene (Spiro-OMeTAD) based solid-state dye-sensitized solar cells (ss-DSSCs). The doping mechanism consumes Li(+) during the device operation, which poses a problem, since the lithium salt is required at the dye-sensitized heterojunction to enhance charge generation. This compromise highlights that new additives are required to maximize the performance and the long-term stability of ss-DSSCs.