•Magnetic particles in solid phase extraction for metal determination.•Synthesis, characterization, classification and applications of MPs.•On-line implementation in SIA, LOV and microfluidic systems.•Critical evaluation of on-line column packing in MSPE. The use of magnetic materials in solid phase extraction has received considerable attention in recent years taking into account many advantages arising from the inherent characteristics of magnetic particles. Magnetic solid phase extraction (MSPE) methodology overcomes problems such as column packing and phase separation, which can be easily performed by applying an external magnetic field. The use of magnetic particles in automatic systems is growing over the last few years making the on-line operation of MSPE a promising technique in the frame of green chemistry. This article aims to provide all recent progress in the research of novel magnetic materials as sorbents for metal preconcentration and determination coupled with different detection systems as well as their implementation in sequential injection and microfluidic systems. In addition, a description of preparation, characterization as well as applications of various types of magnetic materials, either with organic or inorganic coating of the magnetic core, is presented. Concluding remarks and future trends are also commented.