Substituting isoelectronic B–N units for C=C units in π-conjugated systems produces novel materials with structural similarities to all-carbon frameworks but fundamentally altered electronic and optical properties. Further, the co-occurrence of excited states with different symmetry (π-π* and n-π*) should facilitate effective spin-orbit coupling and enhance ISC and RISC processes. (El‐Sayed, 1963). Though BN/CC isosterism has been known for several decades, this concept has yet to be demonstrated. Our group has developed highly sought-after deep-blue delayed fluorescent materials by exploiting the BN/CC isosterism (Front Chem. 2020) and topochemistry (Angew.Chem.Int.Ed. 2018). We have also developed a new strategy for the rational design and construction of novel materials by replacing the carbon-carbon double bond in tetraarylethylene systems with an isoelectronic boron-nitrogen unit (J. Mater. Chem. C, 2016). For the first time, this approach led to the identification of the intriguing aggregation-induced emission enhancement (AIEE) and mechanoluminescence properties of tetra-arylaminoboranes (TAAB) (Organometallics, 2017 and J. Mater. Chem. C, 2017). We adopted a similar strategy to develop multifunctional molecular materials showing triboluminescence (TL) and temperature sensing (Chem. Commun., 2017; Angew.Chem.Int.Ed. 2019). As part of the ongoing program, we studied the crystalline phase-dependent chiral photoluminescence switching in amino boranes with chiral pendants. Enantiomerically pure amino boranes show stronger luminescence than the racemic compound. Interestingly, a rare event of mechanical pressure-induced color switching and inversion of CPL was observed. Detailed steady-state, time-resolved optical studies, together with microscopic and computational studies, unveil that the chiral ordering in solid-state plays a vital role in controlling their optical properties. This is the first example of B-N-based chiral AIEgens showing considerably high ϕF, glum, and switchable CPL features to our knowledge (Org. Lett. 2023., Chem.Eur.J. 2023, Adv. Optical Mater.2023., Chem Science, 2022). We will also discuss the preliminary results of studies on phosphoramide-based chiral AIEgens.