BOPAM exhibits high fluorescence quantum yields, along with exceptional photostability, rendering it a promising platform for applications as fluorescence sensors. However, the development of BOPAM-based fluorophores with extended emission wavelengths remains limited, and the underlying mechanisms of fluorescence quenching via the population of dark twisted intramolecular charge transfer (¹TICT) excited states are not yet fully understood. To address these gaps, we synthesized a series of BOPAM derivatives by incorporating electron-donating groups at the boron atoms and the phenyl rings of the BOPAM core. The introduction of bromide, phenyl, and naphthyl groups preserved the intrinsic locally excited (¹LE) emission of BOPAM. In contrast, the incorporation of diphenylamine (BP-DA) and triphenylamine (BP-TA) moieties resulted in a red-shifted emission, attributed to an enhanced intramolecular charge transfer (ICT) process. Notably, in acetonitrile, BP-DA exhibited weak fluorescence originating from a ¹TICT state, which was populated via the S₂ → ¹TICT transition. Furthermore, the emission observed from BP-TA was associated with a higher-lying excited state, likely the initially populated S₂ state possessing a ¹LE character. These findings not only introduce novel red-emissive BOPAM-based fluorophores, but also offer valuable insights into the role of the S₂ state in governing fluorescence quenching mechanisms in BOPAM derivatives.