Dye-sensitized solar cells (DSSCs) are generally viewed as next generation photovoltaic devices. Electrospun TiO2 nanofibers (NFs) film can be used to construct photoanode for DSSCs. A systematic strategy to optimize such a novel photoanode material of DSSCs was elaborated in this paper. A main drawback of NFs photoanode is the poor adhesion of ceramic NFs film to its conductive glass substrate. This problem can be well solved by sandwiching a transition layer between the overlaid NFs film and the underlaid glass substrate through an interfacial spin-coating pre-treatment. After electrospinning, a controllable calcination is also indispensable for obtaining an ideal nanofibrous mat with good morphology and adhesion. The choice of calcination parameters including temperature, holding time, and heating rate was discussed in detail. In addition, a surface TiCl4 post-treatment can further improve adhesion as well as strength for the NFs photoanode film. And the performance of the resulting DSSCs will benefit from the TiCl4 post-treatment. Copyright (c) 2013 John Wiley & Sons, Ltd.