Ever since the first organic-inorganic hybrid halogen perovskite solar cell was first used as a photo-voltaic material in 2009, reports on this type of solar cell have grown exponentially over the years. Up till May 2014, the photo-energy conversion efficiency of the perovskite solar cell have already achieved an efficiency approaching 20%. Surpassing the efficiency achieved by organic and dye synthesized solar cell, the perovskite solar cell is in good hope of reaching the efficiency compatible with that of mono-crystalline silicon solar cell, thus it is going to be the star in photo-voltaic industry. In a perovskite solar cell, the film-formation and electron-mobility in the electron transfer layer can dramatically affect its efficiency and life-span. Especially in the up-right structured device, the mesoscopic structures of the electron-transfer layer will directly influence the growth of the perovskite layer. The present researches of electron transport materials mainly focus on three aspects: (1) How to improve the instability in mesoporous TiO2-mesosuperstructured solar cells, that arises from light-induced desorption of surface-adsorbed oxygen. (2) How to obtain TiO2 or other electron transport materials at low temperature (sub 150 ℃) in order to be applicatable in flexible devices. (3) How to substitute the mesoporous TiO2 or compact TiO2 transport layer by organic or composite materials. This article devides the materials that are used to make the electron-transfer layer into three distinct groups according to their chemical composition: i.e. metal oxides, organic small molecules, and composite materials, and introduces about the role they play and the recent development of them in constructing the perovskite solar cell.