Mesogenic phthalocyanine has been demonstrated as promising small molecules for use in bulk heterojunction (BHJ) organic solar cells (OSCs). Particularly, the BHJ OSCs utilizing non-peripherally substituted octahexyl phthalocyanine (C6PcH2) mixed in various fullerene derivatives showed relatively high photovoltaic performance with PCEs exceeding 4.2% [1, 2]. Nevertheless, other hybrid structures of phthalocyanine such as non-peripherally substituted octahexyl tetrabenzotriazaporphyrins (C6TBTAPH2), non-peripherally substituted octahexyl tetrabenzodiazaporphyrins (C6DAPH2), non-peripherally substituted octahexyl tetrabenzomonoazaporphyrins (C6MAPH2), and non-peripherally substituted octahexyl tetrabenzoporphyrin (C6TBPH2) have been relatively little studied due to the synthetic challenge inherent in the selective incorporation of specified combinations of the aza and methine groups. Herein, we report the improvement of optical and electronic properties and photovoltaic performance of BHJ OSCs utilizing various phthalocyanine-tetrabenzoporphyrin hybrid macrocyles. By replacement of aza links between the eighteen-π-electron cores of phthalocyanine species by methine links, the highest occupied molecular orbital level and the bandgap energy increased from -5.3 to -4.9 eV and from 1.6 to 1.7 eV, respectively. As a result, the Q-band and B-band of C6PcH2 were red- and blueshifted relative to that of C6TBPH2, respectively. Otherwise, X-ray diffraction patterns exhibited that the mesogenic phthalocyanine comprises columnar stacks of cofacial molecules arranged within a classical two-dimensional hexagonal lattice symmetry (pseudohexagonal structures), and that by replacing aza links by methine links, the arrangement of tetrabenzo(aza)porphyrin was probably changed to be 2-D rectangular [3]. The photovoltaic performance of BHJ OSCs was strongly dependence on the number of aza and methine links between the eighteen-π-electron cores. The BHJ OSC utilizing C6TBTAPH2 mixed in [6,6]-phenyl C71 butyric acid methyl ester exhibited the high power conversion efficiency exceeding 5.3% [3]. Acknowledgments This work was partly supported by Grants-in-Aid (Grant Nos. 24246009 and 25107719) for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan, and by Advanced Low Carbon Technology Research and Development Program from the Japan Science and Technology Agency (JST-ALCA). Quang-Duy Dao was supported by JSPS Postdoctoral Fellowship Program for Foreign Researchers (No. P14051). [1] Q.D. Dao et al., Org. Electron. 14 ( 2013) 2628. [2] Q.D. Dao et al., Appl. Phys.Lett., 101 (2012) 263301 [3] Q.D. Dao et al., Submitted to Org. Electron.