The R5E is basically the Mount Rushmore of X99 motherboards, if you want enthusiast gear then it's an excellent choice.
The X99-E WS really offers no advantages over the R5E unless you want to pack that x16/x16/x16/x16 capability with workstation cards to do some serious number crunching. It has the same 3-way/4-way/quad SLI limits as the R5E in terms of graphic/gaming performance, PLX might be able to split and multiply maximum lanes but at the cost of added signal latency - the R5E would always have equal or better SLI/CF performance, although perhaps by a very small margin. The extra lanes on the WS might offer a wider range of possible options for PCIe-form-factor storage devices, if you need tons and tons of ultra-fast parallel storage.
Both mobos have the same Asus OC Socket, so they'll have essentially the same DIGI VRM phases, electrical hardware, heatsinks, and EUFI/BIOS firmware to drive it. Both have the same audio, USB, LAN, etc. The R5E ships with a useful 3T3R WiFi accessory (and now also a USB3.1 card), the WS doesn't. The WS supports JEDEC ECC DDR4, if that's your thing, but the R5E doesn't. Both mobos support the same Core-i7 and Xeon-E5 processors. I expect (hope) that Asus would work hard to support "workstation" products, but I don't know if they do. The "flagship" R5E has aggressive support for extreme DDR4 and general gaming hardware, and I expect that it will continue to command the lion's share of Asus attention until they release a newer and better "flagship" product. You'll find a lot more setup, overclocking, and troubleshooting guides/info for the R5E than for the WS. And these mobos have different styles and colours. The R5E's ROG red angularity is cool enough, but I personally find it somewhat garish and gamey, I would much rather prefer an R5E with the slick glossy/matte black WS look.
But if you don't really plan to use 4-way multi-GPU support and enthusiast overclocking madness ... the basic Asus X99-A is also a fine mobo and (just like the WS) it also has the same Asus OC Socket plus the same pile of onboard hardware. Perhaps not quite as robust when pushed to the extremes, but also a whole lot less expensive.
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