In this article, we report the unique optical characteristics of boron diiminates in the solid states. We synthesized the boron diiminates exhibiting aggregation-induced emission (AIE). From the series of optical measurements, it was revealed that the optical properties in the solid state should be originated from the suppression of the molecular motions of the boron diiminate units. The emission colors were modulated by the substitution effects (λ(PL,crystal) = 448-602 nm, λ(PL,amorphous) = 478-645 nm). Strong phosphorescence was observed from some boron diiminates deriving from the effects of two imine groups. Notably, we found some of boron diiminates showed crystallization-induced emission (CIE) properties derived from the packing differences from crystalline to amorphous states. The 15-fold emission enhancement was observed by the crystallization (Φ(PL,crystal) = 0.59, Φ(PL,amorphous) = 0.04). Next, we conjugated boron diiminates with fluorene. The synthesized polymers showed good solubility in the common solvents, film formability, and thermal stability. In addition, because of the expansion of main-chain conjugation, the peak shifts to longer wavelength regions were observed in the absorption/emission spectra of the polymers comparing to those of the corresponding boron diiminate monomers (λ(abs) = 374-407 nm, λ(PL) = 509-628 nm). Furthermore, the absorption and the emission intensities were enhanced via the light-harvesting effect by the conjugation with fluorene. Finally, we also demonstrated the dynamic reversible alterations of the optical properties of the polymer thin films by exposing to acidic or basic vapors.