In this Research Article, we present our results on the optimization of the TiO2 blocking layer to improve the efficiency of organic and hybrid solar cells and make them more competitive with standard silicon devices. The major aim of the present work is to increase the electrical conductivity within the TiO2 blocking layer to guarantee for efficient charge carrier transport and separation. This is realized by optimizing the calcination processes toward an increase in particle/domain size to increase the unpercolated pathways for charge carriers and to get deeper insight into the morphology of the sol-gel produced films.