Background: Launaea procumbens is an important medicinal plant took its place also in the ingredient of food as preparation of sherbet, leaves in making curries, and as a goat fodder in most of the part of India. Objectives: The present work was aimed at investigating the phytochemicals of methanolic extract of L. procumbens leaves and its isolated mixtures from column fractions. Materials and Methods: The method was successfully developed and two new compounds (chlorogenic acid and 7-hydroxyflavanone) by liquid chromatography (LC)-electrospray ionization (ESI)-MS/MS and four new compounds (lactucin, isorhametin, 1-monopalmitin, and 1-hexacosanol) by ultra-performance liquid chromatography (UPLC)-ESI-quad time of flight (QTOF)/MS in L. procumbens were identified. Identification of compounds by LC-ESI-MS/MS and UPLC-ESI-QTOF/MS was identified based on the accurate mass of pseudomolecular [M+H]+ ion tandem mass spectrometry (MS/MS) data and by comparing retention times, mass spectra, and molecular weights with those published in the literature. Results: The six new compounds, namely chlorogenic acid, 7-hydroxyflavanone, lactucin, isorhametin, 1-monopalmitin, and 1-hexacosanol were identified by in L. procumbens. Conclusion: A total of 26 compounds by gas chromatography-MS and five compounds by LC mass-ESI tandem mass spectrometry (LC-ESI-MS/MS) and seven compounds by UPLC-ESI tandem mass spectrometry/quadrupole-time-of-flight-mass spectrometry (UPLC-ESI-QTOF/MS) technique were identified.