A green non-dispersive ionic liquid based microextraction (ND-ILμE) method was proposed for the preconcentration of trace levels of copper (Cu2+) in artificial saliva extract (ASE) of smokeless tobacco products (SLT). A 100 cm long, narrow glass column containing aqueous solution of Cu/ASE was used to increase phase transfer ratio by providing more contact area between two medium, which drastically improve the recovery of Cu-PAN complex into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6]. At optimum experimental conditions, the detection limit and the enhancement factor were found to be 0.042 μg L−1 and 85, respectively. This method was successfully applied to real samples.