I’m building it from scratch and probably a 100 or so of those pages will be ecommerce.
I would like to create meaningful, normal looking permalinks for aesthetics and SEO.
I would really love to use WordPress for this but I’m concerned about performance issues with this volume of pages.
There are some issues in WP permalinks implementation that introduce scaling issues for large amount of pages and some specific permalink configurations, see Category in Permalinks Considered Harmful.
Other than that it is business as usual – use decent hosting, keep plugins setup efficient, add caching and you will be fine.