We set up an experimental apparatus to investigate the low-energy electron impact with a liquid beam surface, in which a cylindrical liquid beam with a diameter of 25 μm emits as the laminar flow from a microjet and the positively charged ions produced by the electron-impact ionizations are detected with a linear time-of-flight mass spectrometer. We propose a time-delayed mass spectrometry for this apparatus to identify the cationic fragments produced on the liquid surface, in which the application of the ion extracting pulse is delayed with different time intervals after the electron beam pulse. Sensitivity and specificity of the present methodology are demonstrated by the combinational experiments of the gas-phase and liquid ethanol. In comparison with the gas-phase experiments, the ion peaks become much broader in the mass spectra of the liquid beam, primarily due to the molecular evaporation and diffusion. After delaying with about 2 μs, we find that the hydrocarbon ions are ultimately the predominant products in the mass spectra of the liquid ethanol and they are proposed to be produced on the liquid surface. Above observations are in line with the widely accepted picture of the molecular orientation on the liquid surface; namely, the ethanol's CH3-CH2- group on the liquid surface prefers to be oriented outside. Therefore, we demonstrate a new mass spectrometry to explore the molecular structures of the liquid surface.