Phthalocyanines and subphthalocyanines have been considerably researched in both academia and industry for the development of advanced materials such as photosensitizers for organic solar cells, anti-cancer agents for photodynamic therapy, electrochromic devices and among others. For the last decade, we have been interested in phthalocyanines having fluorine(s) at their peripheral positions, due to their specific properties induced by fluorine atoms; in particular, trifluoroethoxy-coated phthalocyanines. This review introduces the synthesis and application of trifluoroethoxy peri- substituted phthalocyanines and subphthalocyanines reported by our research group. The utilities and advantages induced by trifluoroethoxy group onto phthalocyanines and subphthalocyanines are discussed comparing to the well-studied analogues of non-substituted or tert-butyl substituted ones.