Objective Conventional catheter instability and embolization risk limits the adoption of endovascular therapy in patients with challenging arch anatomy. This study investigated whether arch vessel cannulation can be enhanced by a remotely steerable robotic catheter system. Methods Seventeen clinicians with varying endovascular experience cannulated all arch vessels within two computed tomography-reconstructed pulsatile flow phantoms (bovine type I and type III aortic arches), under fluoroscopic guidance, using conventional and robotic techniques. Quantitative (catheterization times, catheter tip movements, vessel wall hits, catheter deflection) and qualitative metrics (Imperial College Complex Endovascular Cannulation Scoring Tool [IC3ST]) performance scores were compared. Results Robotic catheterization techniques resulted in a significant reduction in median carotid artery cannulation times and the median number of catheter tip movements for all vessels. Vessel wall contact with the aortic arch wall was reduced to a median of zero with robotic catheters. During stiff guidewire exchanges, robotic catheters maintained stability with zero deflection, independent of the distance the catheter was introduced into the carotid vessels. Overall IC3ST performance scores (interquartile range) were significantly improved using the robotic system: Type I arch score was 26/35 (20-30.8) vs 33/35 (31-34; P = .001), and type III arch score was 20.5/35 (16.5-28.5) vs 26.5/35 (23.5-28.8; P = .001). Low- and medium-volume interventionalists demonstrated an improvement in performance with robotic cannulation techniques. The high-volume intervention group did not show statistically significant improvement, but cannulation times, movements, and vessel wall hits were significantly reduced. Conclusion Robotic technology has the potential to reduce the time, risk of embolization and catheter dislodgement, radiation exposure, and the manual skill required for carotid and arch vessel cannulation, while improving overall performance scores.