The invention discloses a cathode interface modification material, and a solar cell as well as a preparation method and application thereof. The cathode interface modification material is prepared from poly [9,9-bis(3'-(N,N-dimethylamino) propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) and/or derivatives of the PFN. The organic thin film solar cell comprises a top electrode layer, a cathode interface modification layer, a light absorption active layer, a hole transport layer and a bottom electrode which are sequentially arranged in the set direction, wherein the cathode interface modification layer is prepared from the cathode interface modification material. The cathode interface modification material provided by the invention adopts the PFN with a permanent electric dipole moment to modify the interface of a cathode of the organic thin film solar cell, namely, a suitable electron transport layer is inserted into the organic thin film solar cell, so that a built-in electricfield is effectively enhanced, carrier transport is further improved, and recombination loss is reduced; the cathode interface modification material can reduce the cathode work function, reduce the electron injection barrier and improve the electron injection efficiency, thereby greatly improving the luminous efficiency, service life and stability of the device, and further increasing the cell efficiency.