Abstract Nanostructured materials play roles in different areas of analytical chemistry. Implementation of nanomaterials in liquid-phase microextraction results in a synergic combination yielding enhanced performance. Some significant examples include: carbon nanotubes for improving extraction efficiency; magnetic nanoparticles for retrieving ionic liquids or organic solvents; metal nanoprobes in a solvent microvolume for desalting and ionization in the analysis of proteins and peptides by matrix-assisted laser desorption/ionization-mass spectrometry; in situ generation of noble-metal nanoprobes for extraction of hydride-forming elements prior to their determination by atomic spectrometry; confinement of fluorescent nanoprobes in a microvolume of organic solvent, thereby integrating separation, preconcentration and analyte recognition within a single step; and, solid-phase extraction involving nanomaterials and liquid-phase microextraction in a sequential way. We provide insight into significant advances involving the joint use of nanomaterials and liquid-phase microextraction.