Tricoordinate boron-incorporated π-conjugated systems are widely investigated as optoelectronic materials because of their unique p-π* orbital interactions and high Lewis acidity. Among them, thiophene-fused diborinines are characterized by moderate antiaromaticity and extended conjugation. In this work, we have developed two new dithienodiborinines with C2h and C2v symmetries, which exhibited completely different optical properties. The thiophene-fused diborinines synthesized in this study showed excellent fluorescence properties both in solution and in the solid state, with quantum yields of up to 95%. The high antiaromaticity enhanced the Lewis acidity of the boron centers, as proven by the large association constants with fluoride ion estimated from titration experiments. The high Lewis acidity and the superior luminescence property have enabled their application as fluorescent sensor materials for the detection of ammonia vapor.