Tian Lu's dissertation describes major advances in ultrathin-layer chromatography (UTLC), liquid chromatography and surface-assisted laser desorption ionization (SALDI), and matrix-enhanced SALDI (ME-SALDI) mass spectrometry. Lu describes the fabrication of electrospun polyvinyl alcohol (PVA) UTLC plates using an in-situ crosslinking electrospinning technique. The author improved the efficiency of PVA plates greatly compared to the efficiency of silica HPTLC plates. Also highlighted in this thesis is an edge-plane based ordered-carbon surface that provides unique selectivity in liquid chromatography. Further developments include polar analytes, such as amino acids, nucleotides and nucleosides which can be well-retained and separated in the edge-plane ordered-carbon stationary phase. Also, the author studied and detected mass spectra of organic polymers as high as 900,000 Da, the highest molecular weight that has been studied by SALDI to date using the carbon nanofibrous substrate. This thesis has led to a number of publications in high-impact journals.