Triarylboranes have attracted significantly increasing research interest as a remarkable class of photoelectronic pi-electron materials. Because of the presence of vacant p orbital on the B center, the boryl group is a very unique electron acceptor that exhibits not only electron-accepting ability through p-pi* conjugation but also high Lewis acidity to coordinate with Lewis bases and steric bulk arising from the aryl substituent on the B center to get enough kinetic stability. Thus, the incorporation of a trivalent B element into pi-conjugated systems is an efficient strategy to tune the electronic and stereo structures and thus the photoelectronic properties of pi-electron systems. When an electron-donating group, such as amino, is present, triarylboranes would likely display intramolecular charge-transfer transitions. These kinds of molecules are often highly emissive. In addition, the geometry of the molecules has a great impact on the emission properties. In this Forum Article, we herein describe our recent progress on the charge-transfer emitting triarylborane pi-electron systems with novel geometries, which substituted pi-system with amino groups at the terminal positions, the o,o'-substituted biaryl pi-system with boryl and groups at the o,o'-positions, a triarylborane-based BODIPY system, and a B,N/S-bridged ladder-type pi-system. We mainly put the emphasis on the molecular design concept, structure property relationships, intriguing emission properties and great applications of the corresponding triarylborane pi=systems. include the lateral borylamino