The present invention provides a cis-stilbene/fluorene derived photoelectric material having hole-blocking characteristics, comprising a cis-stilbene/fluorene derivative formed by a cis-stilbene based compound and a fluorene based compound, and having glass transition temperature between 105 DEG C and 130 DEG C, thermal cracking temperature between 385 DEG C and 415 DEG C, reversible electronic transmission characteristics and superexcellent charge carrier balanced transmission characteristics. Experimental results also confirm that external quantum efficiency, current efficiency, power efficiency, maximum brightness and component life of a yellow fluorescence, green phosphorescence, yellow phosphorescence and red phosphorescence organic light-emitting diode by using the cis-stilbene/fluorene derived photoelectric material as an electronic transmission layer are obviously superior to a prior art or commercialized yellow fluorescence, green phosphorescence, yellow phosphorescence and red phosphorescence organic light-emitting diode.