A neuromodulation system includes neuromodulation electrodes on an electrode support that is positionable within a blood vessel for transvascular stimulation of target nerves. Cathode surface area, cathode-to-anode spacing, and other parameters are selected for capture of specific types of nerves (sympathetic, parasympathetic, and/or mixed nerves), nerves located at larger or shorter distances from the vascular wall, and also for proper nerve capture for the targeted types of nerves.