Two novel types of covalently ether-linked porphyrin–phthalocyanine (Por–Pc), heterodimer and heteropentamer, connected through the meso phenyl group of the porphyrin have been synthesized for the first time. The Por–Pc heterodimer and heteropentamer have more delocalized π-electrons and therefore their conjugated degree is higher. In addition, these compounds possess better solubility and a wider light absorption than typical single porphyrins and phthalocyanines. Solar cell devices based on as-synthesized porphyrin–phthalocyanine heterodimers and heteropentamers as donor materials and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as the acceptor material are prepared and show a noticeably better performance. The suitable ZnPor–(O–ZnPc)4 : PCBM weight ratio for photovoltaic devices is 4 : 1 and the highest photovoltaic properties are achieved based on ZnPor–(O–ZnPc)4 : PCBM (4 : 1) annealed at 140 °C in a vacuum for 20 min. The highest PCE is 2.08.
