The rhodium-catalysed ortho-selective carbenes insertion strategy to activate the non-acidic sp2 Csingle bondH bond of β-carboline and isoquinoline scaffolds was developed. This transformation endows facile fabrication of Csingle bondC bond with high atom economy, pleasant yields and wide functional group tolerance exploiting directing properties of pyridinic nitrogen. In this protocol, diazo compounds of diethyl malonate, dimethyl dimedone and oxindole are tested as carbene source with the release of environmentally benign N2 gas as the by-product. Moreover, to perceive mechanistic insights, ESI-MS studies were conducted, and the key intermediates associated with this transformation were identified. In addition, the metal-free construction of planar polycyclic indolizine-indole frameworks has been accomplished from the synthesized products. Furthermore, the neoplastic and fluorescence properties of Csingle bondN annulated compounds were also determined.