Photoluminescent liquid-crystalline (PLLC) molecules, which can easily tune the PL behavior through the crystal (Cry)–LC phase transition, have attracted significant attention. Previously, we have demonstrated that the incorporation of a semifluoroalkoxy chain into π-conjugated mesogen is a promising approach for developing PLLC molecules with PL and SmA LC characteristics. We focused on the LC and PL characteristics of the molecules induced by the semifluoroalkoxy chain and fluorinated tolanes in the condensed phase. In this study, we developed cyano- or ethoxycarbonyl-terminated donor-π-acceptor-type fluorinated tolanes containing a semifluoroalkoxy flexible chain. The cyano-terminated fluorinated tolanes exhibited intense light-blue photoluminescence in the crystalline phase and did not exhibit any LC phase. In contrast, blue photoluminescence in the ethoxycarbonyl-terminated analogs was slightly weak; however, they exhibited Cry–SmA phase transition during the heating and cooling processes. The PL intensity of the ethoxycarbonyl-terminated fluorinated tolanes significantly decreased in the SmA phase; however, their PL colors changed during the Cry–SmA phase transition. This indicates that the developed tolanes are promising temperature-dependent PL materials, such as PL thermosensors or PL thermometers.