Four different meso‐substituted trans‐homoporphodimethenes containing four five‐membered heterocycles connected through two sp3 meso carbon atoms in a trans fashion and three sp2 meso carbon atoms were synthesized in decent yields through the condensation reactions of 1 equiv. of an appropriate 2,3‐dithienyl‐2‐butenediol with 1 equiv. of meso‐(p‐nitrophenyl)dipyrromethane under mild acid‐catalyzed conditions. All of the trans‐homoporphodimethenes were characterized by HRMS as well as 1D and 2D NMR spectroscopy techniques, and the structure of one of the trans‐homoporphodimethenes was determined by X‐ray crystallography. The crystal analysis indicated that the macrocycle is highly distorted owing to the presence of two meso sp3 carbon atoms and attains a boat conformation. Anion‐sensing studies indicated that these macrocycles can be used as selective fluorescence turn‐on sensors for toxic CN– ions. The trans‐homoporphodimethenes readily form BF2 complexes through treatment with BF3·OEt2 in toluene in the presence of diisopropylethylamine at 70–80 °C for 4 h. The BF2 complexes of the trans‐homoporphodimethenes showed fluorescence bands bathochromically shifted by ca. 80 nm compared with that of BODIPY (4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene) as well as large Stokes shifts.