Phenylmethanimine is an aromatic imine with a twofoldr elevancei nc hemistry:o rganic synthesis and astrochemistry.T ot ackle both aspects, am ultidisciplinary strategy has been exploited and anew,easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, basedo nt he thermal decomposition of hydrobenzamide, with as tate-of-the-artc omputational characterization of phenylmethaniminel aidt he foun-dationfor its first laboratory observation by means of rotationale lectric resonance spectroscopy.B oth E and Z isomers have been accurately characterized, thus providing ar eliable basis to guide futurea stronomical observations. Af urther characterization has been carried out by nuclear magnetic resonance spectroscopy,s howingt he feasibility of this synthetica pproach in solution. The temperature dependence as well as possible mechanismsofthe thermolysis processh ave been examined.