Poly(9-vinylcarbazole), PVK, has been the object of study due to its versatility in polymerization methods. It presents high thermal and photochemical stability and high charge mobility. In the present work, different bimodal high molar mass PVKs were synthesized by cationic polymerization with high yields, above 80 %, and the polymer properties were investigated. The obtained PVKs presented degradation temperatures above 460 °C. The syndiotacticity was around 60 %, and the polymers were amorphous. The glass transition temperature achieved 238 °C. The samples revealed a bandgap value of around 3.49 eV, lower than that reported in the literature. The AFM analysis shows that all the PVK films are smooth, with good substrate coverage and low roughness values. The polymers were evaluated as emitting materials in OLEDs assembled using PVK as a single electroluminescent layer, and the performance was compared to an OLED containing a commercially available PVK. The photoluminescence spectrum presented only a broad emission peak near the visible region at 360-a480 nm. The turn-on voltage (V_on) of all synthesized polymers was lower, while luminance (L_max) and current efficiency values (η_curr) were higher than those obtained using the commercial PVK.