Summary: Polyurea with exotic porous structures has been synthesized by the interfacial polymerization between hexane and a series of 1‐alkyl‐3‐methylimidazolium room‐temperature ionic liquids (ILs). Scanning electron microscopy micrographs of the polyurea show a macroporous morphology of aggregated polymer particles with sizes around 200 nm and pore sizes between 100 to 500 nm. The geometry of the polymer particles and the pore size vary with the ILs employed. X‐Ray diffraction shows ionic‐liquid‐induced suppression of 3D crystalline order in the polyurea products. The microstructures of the polymer together with the FT‐IR results suggest that the observed exotic polymer morphology originates from interactions between the ionic liquid and the polymer.