In this paper, a new type of low molecular weight gelators (LMWGs), C2-symmetric benzene-based hydrogel (C2-BHG) with a 1,4-dimine benzene was self-assembled on glassy carbon electrode (GCE) and mica surface based on the hydrogen bond or hydrophobic interaction. Atomic force microscopy (AFM) characterization demonstrated the formation process of the C2-BHG hydrogel layer from particles to clusters, and finally to interconnected fiber network gel. The C2-BHG hydrogel layer resulted in the increase of the hydrophilicity of GCE surface. The C2-BHG modified GCEs (C2-BHG/GCE) with different assembly time were studied by cyclic voltammetry and electrochemical impedance spectroscopy in the presence of Fe(CN)(6)(4/3) redox probe. The rich amide and hydroxyl groups in the gel film make the C2-BHG/ GCE suitable as ultrasensitive sensor for the detection of Cu(II) ions by stripping voltammetry with the limit of detection of 5 x 10(-10) g/L (S/N> 3). Under the optimal conditions, the two linear ranges of Cu(II) ions were found to be 1 x 10(-9) similar to -1 x 10(-7) g/L and 1 x 10(-7) similar to -1 x 10(-4) g/L. The strong coordination interaction of C2-BHG with Cu(II) ions was confirmed by UV-Visible characterization. This new type of C2-BHG modified electrode was promising for highly sensitive Cu(II) ions sensor application due to high stability and excellent selectivity of the analytical signal. (C) 2015 Elsevier Ltd. All rights reserved.