This article reports on effect of solvent vapor annealing on TiOPc thin films and the application on hybrid solar cells based on ZnO/TiOPc with DH-alpha6T as an electron blocking layer. The band gap shows a change for the TiOPc thin film solvent vapor annealed with various solvents, which may be due to the phase transition from amorphous to alpha-phase, beta-form or alpha+beta-form. The phase separation could be responsible for the variations of the optical properties. No significant change is observed in the pi-pi* transition at various phase behaviors. Device performance of hybrid solar cells could be improved and open-circuit voltage (VOC), short-circuit current (ISC) and power conversion efficiency (eta) were enhanced by solvent vapor annealing, which originated from amorphous TiOPc films transformed into crystalline alpha-phase, beta-form or alpha+beta-form.nbsp At alpha-TiOPc, the device achieved the highest performance with VOC, ISC and eta of 0.57 V, 1.40 mA/cm2, and 0.22 %, respectively, which originated from alpha-TiOPc with the widest red and near-IR absorption band