This study presents the effect of the addition of 0.4 wt.% carbon black (CB) to polyamide 66 (PA66) containing 30 wt.% short glass fibers (GFs) on the behavior of composite thermal crystallization. Composites were studied by differential scanning calorimetry analysis (DSC) at different cooling rates using wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM). This thermal crystallization study highlights the nucleation effect of GFs that promote PA66 crystallization by significantly increasing crystallization kinetics and rates. The activation energies (Eas) calculated by model-free (FWO; KAS) and model-fitting (Kissinger method and C–R method) approaches showed that the combination of both GF and CB decreases the activation energy with respect to neat PA66, meaning that the presence of both additives facilitates crystallization. The Coats–Redfern and Criado methods showed that the crystallization of neat PA66 and related composites follows the second-order reaction, i.e., the decelerated reaction, evidencing compatibility between GFs and the matrix.