Display omitted •A novel monomer containing aromatic Schiff base was incorporated into PET.•Cross-linking reaction occurs among the CHN structure units at high temperature.•Cross-linking promotes char formation and melting viscosity increasing.•PET copolyesters with no-dripping and low smoke release show improved fire safety. Bonding aryl groups with carbon-nitrogen double bond is a critical structural factor for the self-crosslinking of Schiff bases at high temperature. In this study, a novel aromatic Schiff base “5-(benzylidene-amino)-isophthalic acid dimethyl ester (BA)” has been designed as a self-crosslinking monomer for poly(ethylene terephthalate) (PET) based copolyesters (BAnPETs). The cross-linking behaviors, flame retardancy and non-dripping performance of BAnPETs have been investigated by simultaneous thermal analysis (TG-DSC), dynamic rheology, limiting oxygen index (LOI), UL-94 vertical burning and cone calorimetry tests. It is found that BA units can cross-link during combustion resulting in high melting viscosity and enhance char forming for BAnPETs, which endows the copolyesters with excellent flame retardancy and non-dripping behavior. Incorporating of BA with a low content (only 7.7 mol%), the LOI value of copolyester increases from 22.0% to 31.0%, and at the same time it achieves V-0 rating in the UL-94 vertical burning test. The mode action of Schiff bases on flame retardation and anti-dripping of copolyesters also has been investigated, and the results show that the aromatic Schiff base groups can lead copolyesters to form nitrogen-containing cross-linkable networks and further transform into compact char layer during combustion. The char layer which acts as an effective barrier, cuts off oxygen, hinders the volatilization of combustible gas and isolates unburned polymer from fire resource. This work suggests that using Schiff base as a self-crosslinkable monomer is a new and effective way for fire-safe polymeric materials.