In my opinion, for getting out there and doing the 'smoozing startup activities', the best person for the job is you: the founder himself. Who better knows your startup and its goals, and who else best stands to personally benefit the most from these activities other than you?
Regarding UX, as a designer, I've always been skeptical of people who label themselves as experts. It's not that I don't recognize its importance--depending on your application, product, website, whatever, it can be critical--I'm just skeptical of those practitioners who present it as some kind of mystical art. Because it's not.
It's hard to say for sure without you providing more information, but chances are you're not designing the next Microsoft operating system. Know your product, know what core value it provides the end user with, follow the KISS principle, and hire qualified designer/developers and you should be off to a good start. This is obviously easier said than done, but improvements can likely be made incrementally over time as user feedback rolls in.
Will having a UX expert on board make that big of a difference? Is that difference worth a fifth of your company? These are questions that only you can really answer in the end.
My obvious bias aside, hopefully I've given some valid insight into why I would hesitate to give 20% of the startup away for something that may not be as important a contribution as you believe. Personally, I would only consider it if he was capable of providing proven connections to investors (and then the UX advice is just a bonus).
But even then I'd think twice about giving such a large chunk away to someone who doesn't exactly sound ready to commit.