Mass spectrometry (MS) is a well established tool for identification of metabolites and proteins. Ionization of these molecules prior to entering an MS is almost carried out by either MALDI (MatrixAssisted Laser Desorption Ionization) or ESI (Electrospray Ionization) method. However, these methods require the sample processing or preparation leading to time consuming and unexpected modifications. Here we reported the detection of metablolites and proteins directly from sample by LAESI-MS. The LAESI technique use the native water in sample to couple the mid-infrared laser radiation into them for instantaneous sampling through plume formation. Ionization of this plume with an electrospray source enables direct MS analysis without sample preparation. Many metabolites were directly identified from serum sample based on accurate masses and isotope distribution patterns from MS. LAESI-MS method was applied successfully for identification of some standard proteins such as human serum albumin, chicken egg white lysozyme, cow heart cytochrome c, and concanavalin A from jack-bean (Canavalia ensiformis).