We report a mass spectrometric access route to analyze nonpolar poorly ionizing synthetic polymers exploiting supercharging technology by chloride attachment via high resolution electrospray ionization mass spectrometry (HR ESI MS). The novel mass spectrometric procedure allows for the characterization of polyhydrocarbons, which include hardly ionizable polymers such as poly(styrene) (PS) (ranging from 1700 to 18 000 g mol(-1)) and for the first time reported using ESI as ionization method poly(1,4-butadiene) (PBD) (ranging from 1000 to 10-000 g mol(-1)). The method is also applied to additional synthetic polymers including poly(2vinylpyriciine) (P2VP) and poly(acrylamide) (PAAm). The powerful chloride attachment enables the detection of,multiply charged polyhydrocarbons (up to quadruply charged). A systematic assessment of the manipulation of these charge states using supercharging agents (sulfolane, propylene carbonate, and m-nitrobenzyl alcohol) is carried out. Our investigatiOns include an assessment of the influence of different ESI solvents (water, acetonitrile, acetone, tetrahydrofuran, dichloromethane, and methanol), water-ddped organic ESI solvents, and the amount of supercharging agent.