Non-isothermal differential scanning calorimetry (DSC) was used to study the influences of particle size daver and heating rate q+ on the crystal growth and decomposition kinetics of amorphous N,N’-bis(3-methylphenyl)-N,N’-bis(phenyl)-benzidine (TPD). The macroscopic crystallization kinetics was found to be strongly dependent on q+. At high q+, the crystal growth proceeded dominantly from the mechanical defects acting as primary growth centers, with the corresponding activation energy being ∼70–80 kJ mol−1. At low q+, the crystalline phase was primarily formed from heterogeneous nuclei, with the activation energy for the growth process being ∼980 kJ mol−1. The prolonged nucleation led to extensive passivation of the surface mechanical defects with respect to their function as direct crystal-growth-accelerating centers. Temperature-resolved in-situ Raman microscopy has confirmed the conclusions derived from the DSC data and helped to identify the residual low-q+ defects-originating crystal growth as proceeding from volume-located micro-cracks. The X-ray diffraction analysis confirmed that TPD crystallizes into an identical phase under all circumstances. The thermal decomposition of TPD was found to proceed in a single step, by simple nth-order reaction kinetics with the activation energy of ∼120 kJ mol−1.