A series of easily prepared Lewis basic ionic liquids were developed as recyclable and efficient catalysts for selective synthesis of 5-aryl-2-oxazolidinones from aziridines and CO₂ without utilization of any organic solvent or additive. Notably, high conversion, chemo- and regio-selectivity were attained when 1-butyl-4-aza-1-azaniabicyclo[2.2.2]octane bromide ([C₄DABCO]Br) was used as the catalyst. Furthermore, the catalyst could be recycled over four times without appreciable loss of catalytic activity. The effects of the catalyst structure and various reaction parameters on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of aziridines producing the corresponding 5-aryl-2-oxazolidinones in good yields and excellent regioselectivities. Therefore, this solvent-free process thus represents an environmentally friendly process for ionic liquid-catalyzed conversion of CO₂ into value-added chemicals. A possible catalytic cycle for CO₂ activation induced by nucleophilic tertiary nitrogen of the ionic liquid was proposed, based on studies using in situ FT-IR spectroscopy under CO₂ pressure.