We present a topology-aware computational framework that enables global collision-free and support-structure-free material extrusion for curved layer multi-axis printing of a range of high-genus and simply connected models. The nature of multi-axis additive manufacturing facilitates continuous variation of build direction, which paves the way for numerous approaches of geometry-based curved layer design. However, due to unawareness of global topological features, prevention of collision between the printer nozzle and the workpiece can either remain uncertain or demand for exhaustive algorithmic approaches, depending on the topological and geometrical complexity of a given mesh model. In this paper, we present a topological analysis framework that draws inspiration from the concepts of Reeb graph and Morse theory, to distinguish between collision-prone and collision-free regions of mesh models. We provide an exact definition for global collision-inducing features in regions of risk and optimise the nozzle orientation vector field to avoid global collisions whilst adhering to the overhang angle constraints. A new shape analysis method is then proposed to find the model orientation which maximises the manufacturability of bifurcating simply connected models. To validate our algorithmic framework, several high-genus and bifurcating simply connected models are printed using a robotic multi-axis printer. The experimental results demonstrate the feasibility and effectiveness of our framework for minimising global collisions in multi-axis curved layer additive manufacturing for a range of mesh models.