In this article, we briefly highlight the use of capillary electrophoresis for sampling, manipulating, and separating extremely small sample sizes. The extraordinary sensitivity that can be obtained by combined capillary electrophoresis‐mass spectrometry is then demonstrated using recent results. We briefly describe the ability to detect noncovalently associated complexes (e.g., double‐stranded DNA) by electrospray ionization‐mass spectrometry, and conclude with recent results that show the potential for using high‐resolution Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry for characterization of biomolecules.