Detection of aromatic amines without derivatization was carried out using a new solid-phase microextraction fiber coated with 25,27-dihydroxy-26,28-(10,100-dioxo-40,70-diaza-30,80-dioxooctamethylene)-p-tert-butylcalix[4]arene (amide bridged-C[4]). The new fiber shows excellent selectivity and sensitivity for the tested amines (aniline, o-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, N-ethyl-m-toluidine, and N,N-diethylaniline). The coating has high thermal stability (up to 380 C) and solvent stability. Experimental conditions, such as extraction temperature and time, pH and ionic strength were optimized. The method proposed here shows good linearity and low detection limits ranged from 1.2 to 40 ng.L)1. Application of this method was demonstrated through the determination of aromatic amines in wastewater from a pharmaceutical plant.