Asymmetric boron complexes composed of (iso)quinolyl-pyrrole ligands possessing triphenylamine unit on the (iso)quinoline or pyrrole moieties were systematically prepared. Their optical properties were investigated in various organic solvents, and they showed solvatochromic properties, which were influenced by the π-structure of the ligands and the position of the electron-donor group. The degrees of changes in the emission-color drastically changed for regioisomeric chromophores 1 and 2. In this study, the solvatochromic properties of the compounds were investigated and described using both experimental and computational results.