The present study deals with the preconcentration and determination of toxic metal ions using p-tetranitrocalix[4]arene (3) appended silica-based new HPLC column. The synthesized material was characterized using Fourier transform infrared and scanning electron microscopy techniques. The sorption characteristics of the HPLC column were investigated for three toxic metals (Cd2+, Hg2+ and Pb2+) in column agreement. The experiments were performed in five steps that were monitored using a UV-visible diode-array detector. However, all the HPLC experimental results were reconfirmed by using atomic absorption spectrophotometer. The effect of concentration on the sorption efficiency of the column was evaluated for all the three metals and the data obtained were investigated using Langmuir, Freundlich and Dubinin-Redushkevich (D-R) sorption isotherms. The value of coefficient of determination (R 2), i.e. 0.99, suggested that the Freundlich sorption isotherm was found to be the best-fit model for all the three toxic metal ions, whereas, mean free energy was calculated from the D-R isotherm as 5.3, 5.7, and 5.8 kJ/mol for Pb2+, Cd2+, and Hg 2+, respectively; suggesting that physical electrostatic force is involved in the sorption process. The developed method was validated for system efficiency, accuracy, and precision. © 2013 Springer-Verlag Berlin Heidelberg.