A new series of (co)polycarbonates bearing pendent azido groups was synthesized by polycondensation of varying molar proportions of 4, 4’-(5-azidopentane-2, 2-diyl) diphenol and bisphenol-A with triphosgene. The chemical structures, compositions and random nature of (co)polycarbonates were confirmed by NMR spectroscopy. Inherent viscosities and number-average molecular weights of (co)polycarbonates were in the range 0.63–0.77 dL g−1 and 35,400–43,400 g mol−1, respectively indicating the formation of reasonably high molecular weight polymers. (Co)polycarbonates could be cast into tough, transparent and flexible films from chloroform solutions. (Co)polycarbonates were further characterized using IR spectroscopy, XRD, TGA and DSC. The thermal crosslinking of (co)polycarbonates bearing pendant azido groups was studied by DSC analysis. Independently, (co)polycarbonates bearing pendant azido groups were exposed to UV irradiation at wavelength of 254 nm and decomposition reaction of azido groups was monitored by FT-IR spectroscopy. The complete decomposition of azido groups was observed with exposure time of 30 min. The formed cross-linked (co)polycarbonates exhibited improved % char yield values compared to parent (co)polycarbonates. The measurement of mechanical properties of representative crosslinked (co)polycarbonates indicated increase in tensile strength and Young's modulus and decrease in % elongation compared to corresponding parent linear (co)polycarbonates. © 2022 Wiley-VCH GmbH.