The recent developments in hollow fiber liquid phase microextraction and dispersive liquid-liquid microextraction are reviewed. Applications of these newly emerging developments in extraction and preconcentration of a vast category of compounds including heavy metals, pesticides, pharmaceuticals and abused drugs in complex matrices (environmental and biological matrices) are reviewed and discussed. The new developments in these techniques including the use of solvents lighter than water, ionic liquids and supramolecular solvents are also considered. Applications of these new solvents reduce the use of toxic solvents and eliminate the centrifugation step, which reduces the extraction time.