A series of MC nylon-6/ polyethylene oxide (PEO) blends were prepared via in-situ polymerization. It was found that addition of PEO delayed the polymerization process of caprolactam. The apparent activation energy and pre-exponential factor increased, indicating that the polymerization reaction became difficult with increasing PEO content. The stress-strain curves of the blends presented strain hardening behavior and increasing elastic deformation stress plateau at low PEO content. Non-isothermal DSC and XRD test indicated that addition of PEO led to a decrease of the crystallization ability of the nylon-6 matrix by reducing crystal grain size and crystallinity, while the crystallization ability of the PEO phase was improved. No co-crystal formed between the two phases. PEO with low content only existed as amorphous state, while with increasing PEO content, PEO can crystallize gradually, forming interfibrillar segregation first, and then forming interspherilute segregation of the blend independently. By addition of PEO, the fracture surface of the blend became rough, displaying character of tough fracture. The interface between nylon-6 phase and PEO phase was diffused, and the nylon-6 matrix around the PEO particles presented fibrous structure, indicating of the good compatibility between them. The toughening mechanism of the blend corresponded to the crazing-shear banding mechanism.