Nowadays, high analytical throughputs are required considering an increasing demand for faster, simple and improved methods to analyze contaminants in a considerable number of samples. Generally, these compounds are present in complex matrices in contact with a high number of interferents becoming their determination difficult at low concentration. In this context, on-line extraction techniques arose to improve the extraction as well as separation power, while minimizing errors related to human sample manipulation. This paper describes a study regarding the development and optimization of columns used as an extraction device in multidimensional liquid chromatography. The main goals were the evaluation of the material used as column body as well as the investigation of the tube dimensions (internal diameter and length) in the extraction performance. Firstly, several tube materials were tested (steel, fused silica, PEEK, among others) being steel whose reported the best performance and was consequently chose for further studies. The investigation about the effects of the columns physical dimensions revealed a linear relationship between performance and the amount of sorbent utilized as extractive phase. However, when different columns with same amount of sorbent were tested results suggests that both i.d. and lengths play an important role in extraction efficiency. The longest columns with lower internal diameter showed the best results favoring the radial as well as axial analytes diffusion into the extraction column. After evaluation of these column variables, applications were carried out employing several different analytes belonging to various chemical classes and practical utilization, in order to reinforce the versatility as well as the robustness of this proposed study.