We investigated the capturing mechanisms of highly charged macromolecular ions of polyethylene glycol electrosprayed onto a metal screen. Our experiments assessed how the charge state, size of the macromolecular ions, and filtration velocity affected the penetration of the ions through the metal screen. The single fiber efficiencies were plotted as functions of the Peclet number and image force parameter. Highly charged molecular ions had much higher collection efficiencies than neutralized macromolecules, suggesting the presence of a strong image force between the ions and metal surface. The single fiber efficiency by image force was proportional to the square root of an image force parameter predicted by theory. When using the prefactor of 9.7 proposed by Alonso et al. (2007), we found fair agreement between the experimental data and theoretical predictions on the collection efficiency of highly charged molecular ions with mobility diameters from 2.6 to 4.8 nm and numbers of electrical charges from 2 to 7. The experimental evidence from our study reveals that image force contributes strongly to the collection of multicharged macromolecular ions by a metal wire screen.