The Water Framework Directive (WFD), Directive 2000/60/EC, was introduced in 2000 with the aim of member countries attaining ‘good status’ in water bodies that are below good status at present, as well as retaining good or better status where it already exists by 2015. According to WFD [1] 41 priority substances and a further 25 priority hazardous substances were identified to be included in water monitoring programmes. These substances can be divided into four main groups: pesticides, volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and metals and trace elements. A standardised, reliable and efficient method, incorporating both sample preconcentration and analysis steps, is required to facilitate these monitoring programmes. As popular techniques currently in use involve solid-phase extraction (SPE), or liquid chromatography (LC), a critical evaluation has been carried out on their applications, with regard to priority pollutants and hazardous substances. SPE is used for sample pre-concentration and cleanup, for removal of specific substances from aqueous solutions, and for the purification of various chemicals, while LC is used for the separation and subsequent detection of analytes.