Laser Desorption/ Ionization-Time of Flight Mass Spectrometry (LDI-TOFMS) is generally used for analysis of organic compounds because this technique generates little fragmentation of molecular ions at ionization. It makes possible to obtain information on molecular weights and molecular structures in organic compounds. In particular, a technique which uses the matrix compounds for enhancing ionization efficiency is well known as Matrix-Assisted Laser Desorption/ Ionization-Time of Flight Mass Spectrometry (MALDI-TOFMS). This technique is widely used in the bio markets owing to its capability of ionizing proteins and peptides with the molecular weights of several thousands to several hundreds of thousands. The MALDI-TOFMS is also utilized for analysis of synthetic polymers. In many cases, LDI-TOFMS and MALDI-TOFMS have been used to estimate the molecular weights of organic compounds in solution. But very recently, techniques of imaging mass spectrometry, which controls the laser irradiation position by two-dimensional scan to acquire mass spectra for visualizing localization of chemical compounds with specific molecular weights, have been improved. The application of this innovative technique is increasingly spreading in the bio markets. The technology of Imaging Mass Spectrometry has been advancing for analyzing biological tissue sections, but in the future, it is expected to develop toward the material science markets. It is noted that various surface analytical techniques are already available in the material science markets. In order to study the advantages of LDI-TOFMS as one of effective surface analysis tools, it is essential to consider the complementary analysis of LDI-TOFMS with the existing surface analytical techniques. In this article, the advantages of using LDI-TOFMS for analyzing organic lightemitting diode material thin films, in accordance with comparison with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS), X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy/Energy-Dispersive X-Ray Spectroscopy (SEM/EDS), have been studied. In addition, since LDI-TOFMS is a destructive analytical technique, the influence on the sample surface caused by LDI-TOFMS was also examined.