This paper shows the capabilities of applying the three-dimensional finite element method (3D-FEM) for designing complex-shaped substation connectors to operate at 765 kVRMS AC. To check this methodology, it was analyzed the feasibility of upgrading a 400 kVRMS substation connector to operate at 765 kVRMS. However, both experimental and simulation results conducted according to the ANSI/NEMA CC 1-2009 standard concluded that although it passed the visual corona test, to ensure a wide safety margin it was desirable an improvement of the electrical behavior of such connector. It was shown that FEM results allowed detecting the peak stress points of the connector regarding the electrical stress thus allowing applying a corrective action. Then, two possible solutions were analyzed, i.e. the use of corona shields and the redesign of the connector assisted by 3D-FEM simulations. Results presented in this work show that both approaches have an excellent behavior in reducing the electric field strength on the connector surface. However, to make the final decision, the production cost of both alternatives was analyzed, thus favoring the redesign option. Next, the redesigned version of the substation connector was manufactured and tested. Experimental results conducted in a high voltage laboratory verified the effectiveness of the methodology and the potential of the proposed system to act as an advanced design tool for optimizing the behavior of complex-shaped substation connectors. Thus, this system allows assisting efficiently the design process while permitting constraining the economic costs