The photogeneration quantum efficiency action spectra of long-lived neutral and charged excitations in films of a ladder-type poly(para-phenylene) were measured. We found that both tripler and polaron action spectra show, in addition to a step function increase at the optical gap, a monotonic rise at higher energies. For triplets this rise is explained by singlet exciton fission into triplet pairs from which the triplet exciton energy in the gap was obtained; this energy was also confirmed by measuring the weak phosphorescence band. For polarons the photogeneration increase at high energies is modeled by a novel hot electron interchain tunneling process. [S0031-9007(99)08980-2].