The fluorescence property of zwitterionic surfactant tetradecylbetaine (C14BE) solutions in the presence of polyvinylpyrrolidone (PVPk30 and PVPk90), or Xanthan (Xc) have been investigated by steady-state fluorescence probe. The intensity ratio of the first and third peaks (I1/I3) of the monomer and that of the excimer to monomer (Ie/Im), and the aggregation number of the aggregates have been monitored. The results showed that C14BE/PVP and C14BE/Xc interactions mostly occur at the micelle surface. The C14BE clusters or micelles are bound to macromolecule chains by electrostatic force for PVP and by hydrogen-bonding for Xc, respectively.