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TMB-5 nucleating agent (NA) treated by different solvents were used as the <i>β</i>-NA of iPP. The effects of temperature on the crystalline structure of different iPP/TMB-5, as well as the crystallization and melting behaviors were investigated. It was found that strong polar solvent treated TMB-5 (TMB-5_DMSO and TMB-5_DMF) could induce more <i>β</i>-crystal at high T_c = 140 °C than the other TMB-5 NAs, while the <i>β</i>-crystal inducing efficiency of untreated TMB-5 (TMB-5_UT) and non-polar solvent treated TMB-5 (TMB-5_LP) is seriously reduced at high T_c = 140 °C. TMB-5_DMSO can induce a high and stable content of <i>β</i>-crystal with K<i>_β</i> = 83–94% within T_c = 90–140 °C, and TMB-5_ODCB can induce a high content of <i>β</i>-crystal with K<i>_β</i> > 91.3% within T_c = 90–130 °C. TMB-5_DMF is the most temperature-sensitive one, but can induce a high fraction of <i>β</i>-crystal with K<i>_β</i> > 92% both at low T_c = 90 °C and high T_c = 140 °C. High temperature pre-crystallization at T_pc = 150 °C tremendously reduces the <i>β</i>-crystal inducing efficiency of all TMB-5 NAs. TMB-5_UT and TMB-5_LP exhibit higher nucleating efficiency than TMB-5_DMSO, TMB-5_DMF and TMB-5_ODCB. During the non-isothermal crystallization process, TMB-5_UT induced <i>β</i>-crystal possesses higher structural perfection and stability, while TMB-5_LP is more likely to induce <i>α</i>-crystal with considerable quantity and stability. The structural perfection and stability of TMB-5 induced <i>β</i>-crystal can be enhanced with appropriate increasing of T_c.