AbstractThe polyamide 12 (PA12) with different crystal forms is prepared with three crystallization paths. The crystal structures and corresponding thermal properties are systematically investigated. The results reveal that an α-form and a mixed (α + γ)-form of PA12 can be obtained by casting at 30°C and (40–80°C), respectively. Meanwhile, the γ-form of PA12 can be obtained by both casting at 90°C and slow melt cooling. However, the γ′-form is obtained only by melt quenching. Both the γ and γ′ forms of PA12 exhibit a single melting peak, whereas the α-form exhibits two melting peaks. The higher peak is attributed to the melting of γ-PA12, which originates from the melting–recrystallization of the α-PA12. It is found that the tensile properties of PA12 depend on the crystal forms. Both the γ and γ′-PA12 are strong and tough polymer materials, while α-PA12 is a strong but brittle polymer material.