Conformational behaviors of syndiotactic polystyrene (sPS) in chloroform were investigated by detecting its concentration dependence of intrinsic fluorescence in the range from 25 to -62 degrees C. For the dimer emission, the coexistence of T-shaped configuration with sandwich configuration was observed and the contribution of sandwich configuration increases with increasing sPS concentration in the system. In addition, three conformations are observed in sPs/cHCl(3) systems: (I) coil phase; (II) coil-to-helix transformation; (Ill) helix-to-network transformation. The conformational ordering of polymer chain in super dilute sPS/CHCl(3) systems during isothermal process indicated that micro-gel formed when the concentration was higher than 0.2 g L(-1) and single helix formed at 0.09 similar to 0.2 g L(-1) proceeds through a unimolecular or self-organization mechanism and no helical aggregates were found. The helix was formed by clustering of several chain segments when the polymer concentration was below 0.09 g Moreover, a model was proposed to describe the elasticity of sPS/CHCl(3) systems near and beyond the critical percolation concentration. (C) 2011 Elsevier Ltd. All rights reserved.