Thin films of the emeraldine base (EB) form of polyaniline containing different forms of hydroquinones (hydroquinone, HQ(1); tetrafluorohydroquinone, HQ(2); tetrahydroxy-1,4,-quinone, HQ(3)) were cast from the solutions of EB/HQ(1,2,3) in N-methylpyrrolidinone (NMP), Their properties were studied using optical micrography, UV-vis, and infrared absorption. It was found that hydroquinones act as molecular dopants of PANI by donating protons from their OH groups to the imine centers of the polymer and thus provoking a conversion of EB toward the emeraldine salt (ES). The extent of this conversion process is determined by the concentration of HQs and their ability to transform into the anion. Other important parameters are the temperature of drying and the time of storage of the liquid substance before casting, Because of the presence of at least two OH groups in HQ molecules, they can react with two or more imine centers of the polymer, thus bridging different polymer chains and provoking their ordering. Drying of the macroscopically ordered EB/HQ(1,2,3) liquid allows us to fix this ordering and to observe the nucleation and growth of spherulite crystals. Thus, HQ molecules play a double role in determining the structure and properties of emeraldine base. They, on one hand, produce protonation of the imine bonds of the polymer, similar to the mechanism of acid anion doping, and on the other hand, they operate as agents, causing the reorientation of conformational planes in polymeric chains and their mutual ordering.