Para-bisguanidinyl benzene I and its N-permethylated derivative 2 are both sufficiently strong bases to afford not only the monocations [1+H](+) and [2+H](+), but also the doubly protonated ions, [1+2H](2+) and [2+2H](2+), in the gas phase. The title ions generated via electrospray ionization are probed by collision-induced dissociation experiments which inter alia reveal that the dicationic species [1+2H](2+) and [2+2H](2+) can even undergo fragmentation reactions with maintenance of the 2-fold charge. Complementary results from density functional theory predict PAs above 1000 kJ mol(-1) for the neutral compounds, i.e., PA(1) = 1025 kJ mol(-1) and PA(2) = 1067 kJ mol-1. Due to the stabilization of the positive charge in the guanidinium ions and the paraphenylene spacer separating the basic sites, even the monocations bear sizable proton affinities, i.e., PA([1+H](+)) = 740 kJ mol(-1) and PA([2+H](+)) = 816 kJ mol(-1).