In this study, a novel branched polyamide 6 has been synthesized via the hydrolytic ring-opening co-polymerization of ε-caprolactam (CPL) and α-Amino-ε-caprolactam (ACL). The NMR characterization proves the existence of a branched chain structure. The rheological test determines that there is a remarkable increase in the melt index (MFR), zero shear rate viscosity, and storage modulus in the low-frequency region. The shear-thinning phenomenon becomes more obvious. The thermal properties tested by differential scanning calorimetry (DSC) show that the melting point and crystallinity of co-polymers decrease with the incorporation of ACL. However, the crystal structure of the samples only exhibits a slight change. When the ACL content in the feed is 1 wt%, the tensile strength and fracture elongation rate of the co-polymers show a significant enhancement.