The invention provides a simple, rapid and cost-effective metal oxide-assisted laser desorption/ionization mass spectrometry (MOALDI MS) without the addition of light-absorbing organic-matrix, comprising the use of (a) an inorganic metal oxide with light absorbing capability as an assisting material to render desorption/ionization of samples in laser desorption/ionization mass spectrometry and (b) a citric acid buffer as the proton source for enhancing the ionization efficiency for analytes. Metal oxide assisting materials is not only restricted to the uses of films. Metal oxide nanoparticles are also suitable to be used as the assisting materials. Low matrix background, stable surface feature, homogeneous sample deposition, and wide detectable mass range are the merits of MOALDI MS.