The invention provides a double-reflection type flight time mass spectrometric photoelectron velocity imaging instrument. The double-reflection type flight time mass spectrometric photoelectron velocity imaging instrument is provided with a laser sputtering ion source, a cooling ion trap, a flight time mass spectrum and a negative ion photoelectron velocity imaging system; the laser sputtering ionsource is used for generating cluster ions, after entering the cooling ion trap for imprisonment and cooling, and the generated cluster ions are accelerated vertically by an accelerating field and then enter the flight time mass spectrum. The negative ion photoelectron velocity imaging system is used for detecting emitted photoelectrons, and a photoelectron spectroscopy with a neutral cluster electronic structure is obtained. The laser sputtering ion source is used for generating cluster ions, after entering the linear ion trap for imprisonment and cooling, the generated cluster ions are accelerated vertically by an accelerating field and then enter the flight time mass spectrum, and the intensity distribution of the generated cluster ions is obtained through mass spectrometric detection.After the mass spectrum is analyzed, specific cluster negative ions are selected, and through the interaction with desorption laser, neutral molecules and the photoelectrons are generated. The negative ion photoelectron velocity imaging system is used for detecting the emitted photoelectrons, and the photoelectron spectroscopy with the neutral cluster electronic structure is obtained.