• A new vector field-based curved layer slicing and printing path planning method is proposed. • A quantitative optimization model is established to find the optimal filament orientation and printing orientation vector fields. • Multi-factors including support-free requiement, collision-free condition, and mechanical performance are considered. • A continuous printing path planning algorithm is developed to reduce the number of nozzle retractions. The emergence of multi-axis printing systems provides a new solution to print complex parts. However, the current process planning methods fail to balance the support-free requirement, the collision-free condition, as well as the mechanical performance at the same time when printing parts with complicated features. This paper proposes a new curved layer slicing and continuous printing path planning method that considers these factors. The proposed method makes use of two mutually orthogonal unit vector fields embedded on the tetrahedral mesh of the part: the filament orientation vector field and the printing orientation vector field, which indicate the filament orientation and the nozzle orientation at each position during the printing process respectively. A quantitative optimization model is established to compute the two optimal unit vector fields. Then a monotonically increasing scalar distance field is generated by integrating along the optimal printing orientation vector field, and the isosurfaces of the distance field can be used to naturally slice the part into curved layers. Finally, at each isosurface, a continuous printing path is planned along the optimal filament orientation field by interpolating isolines of a surface embedded scalar distance field. Both the simulation and physical experiments were conducted to confirms the effectiveness of the proposed method and its advantage over the existing methods in balance different factors including support-free condition, collision-free requirement, and mechanical performance.