Provided are thiophene-containing organic photoelectric materials represented by structural formula (1). The materials are thiophene compounds having multiple thiophene rings and cyano groups, useful in solar cell applications. One primary compound, for example, derivative of dicyanoethenyl quinquethiophene is well suited for application as electron donor material. Preparation methods of these thiophene-containing organic photoelectric materials and solar cell devices containing the above thiophene-containing organic photoelectric materials also are provided. Due to the fact that thiophene rings and cyano groups are included, the above thiophene-containing organic photoelectric materials have broader spectra respondence, better thermal stability and environmental stability.