Bulk, solventless anionic ring-opening polymerization (AROP) of ε-caprolactam (CPL) with high yields, without side products and with short reaction times, initiated by caprolactamate-carbamoylcaprolactam initiating systems belong to green polymerization processes, leading to poly(ε-caprolactam) (Polyamide 6, PA6, Nylon 6). However, the effect of post-polymerization heat (i.e., slow, technically feasible cooling) on the fundamental characteristics of the resulting polymers such as yield and molecular weight distributions (MWDs) have not been revealed thus far. Significant post-polymerization effect was found by us in terms of both monomer conversions and MWDs by carrying out CPL polymerization with industrial components under conditions mimicking thermoplastic reaction transfer molding (T-RTM). Remarkably, higher monomer conversions and molecular weights (MWs) were obtained for Polyamide 6 samples prepared without quenching than that for the quenched polymers at the same reaction times. Independent of quenching or non-quenching, Mn of the resulting polymers as a function of conversion fell in the theoretical line of quasiliving AROP of CPL. At high monomer conversions, significant increase of the MW and broadening of the MWDs occurred, indicating pronounced chain−chain coupling. These findings have fundamental importance for designing processing conditions for in situ polymerization processes of ε-caprolactam by various techniques such as T-RTM, reaction injection molding (RIM), and other processing methods of Polyamide 6.