In the next-to-minimal supersymmetric standard model (NMSSM), the unique λSH_uH_d in the superpotential gives rise to a coupling involving the lighter pseudoscalar Higgs boson and a pair of charged or neutral Higgsinos, even in the limit of zero mixing between the two pseudoscalar Higgs bosons. We study the associated production of a very light pseudoscalar Higgs boson with a pair of charginos. The novel signature involves a pair of charged leptons from chargino decays and a pair of photons from the pseudoscalar Higgs boson decay, plus large missing energy at the LHC and ILC. The signal may help us to distinguish the NMSSM from MSSM, provided that the experiment can resolve the two photons from the decay of the pseudoscalar Higgs boson.