Here, we first report a study on coumarin 500 and liquid crystal including polyacrylonitrile nanofibers in terms of synthesis, characterizations, and supercapacitor performances. SEM, POM, FTIR, and DSC measurements showed that liquid crystal was inserted into the fine polyacrylonitrile nanofibers successfully. Because a strong molecular interaction took place between coumarin 500 and liquid crystal and coumarin 500 was sensitive to the polarity of the medium, the liquid crystal behaved as a guide material for coumarin 500, and it was expected that coumarin 500 was oriented by the director of the liquid crystal along the core of the fiber. The average polyacrylonitrile nanofiber size was between 0.19 to 0.25 μm, and liquid-crystal-doped and liquid-crystal+coumarin-500-doped fibers exhibited a similar distribution, which is approximately in the 0.30 to 0.60 μm interval. This proved that the fibers maintained their structure after modifications. Electrochemical evaluation of the different composite nanofibers showed that there was not a significant current increase upon liquid crystal addition into polyacrylonitrile nanofibers at voltammograms. C_s values were enhanced after the coumarin 500 addition into liquid-crystal-doped nanofiber and obtained as 410.60 F/g with a specific energy value of 57.03 Wh/kg. Additionally, the long-term charge–discharge test of the liquid-crystal+coumarin-500-doped polyacrylonitrile graphite electrode showed a very steady distribution between 100th and the 2500th cycles with a 14.12% C_s deviation. This is attributed to the stable and robust network of the PAN nanofiber and the synergetic effect between liquid crystal and coumarin 500 in the nanofiber net.