We incorporated a thin but structurally dense TiO2 layer prepared by atomic layer deposition (ALD) as an efficient hole blocking layer in the TiO2 nanofiber based solid-state dye sensitized solar cell (ss-DSSC). The nanofiber ss-DSSCs having ALD TiO2 layers displayed increased open circuit voltage, short circuit current density, and power conversion efficiency compared to control devices with blocking layers prepared by spin-coating liquid TiO2 precursor. We attribute the improved photovoltaic device performance to the structural integrity of ALD-coated TiO2 layer and consequently enhanced hole blocking effect that results in reduced dark leakage current and increased charge carrier lifetime.