Normally, VNAs work as sweeping lock-in amps. I would not expect it have any signal-generating capability beyond 1 mW continuous wave (and below for handheld models). If you want it just as a reference source, it is quite an expensive source, if something returns from your circuit... And again, it is referenced for itself, so I am not sure how good it is as a constant reference. But since it has high precision in phase measurement, phase noise should be pretty low. You should check manuals, or maybe visit Keysight support for consultation.
if you need just a simple amplitude pulse-code modulation, any pin-diode switch will do it; or use simple push-pull switches for better performance. You will need some clock generator, a network of fast registers for generating your code, and a TTL-compatible buffer for connecting to the switch.