VTK is mainly focused on visualization (frontend). It includes some computational geometry functions for convenience (for example, Delaunay triangulation). It is better suited for viewing MRI scans, visualizing large datasets, or converting point clouds / bags from one format to another, for example.
CGAL is focused on computational geometry (backend). To view the result, you will need some type of interface (for example, OpenGL, VTK). It is best suited for molecular biology, astronomy, architectural design, for example.
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