Identification and quantification of metabolites occurring within specific cell types or single cells of plants and other organisms is of particular interest for natural product chemistry, chemical ecology, and biochemistry in general. The integration of studies at the gene, transcript, protein and metabolite levels in localized regions will provide useful information for the understanding of biology as a system. In this review, we summarize the latest developments in the analysis of metabolites present in small samples, micrometabolomics, dealing with sample preparation methods, with focus on laser-assisted microdissection, and the analytical technologies used. Mass spectrometry (MS) and nuclear magnetic resonance (NMR) are among the most emergent technologies in metabolomics, enabling the shortest route toward metabolite identification.