It's best to always check VMware's compatibility lists when installing their products. This applies to both hardware and software.
If you're looking to build a test lab, use nested virtualization: create one or more ESXi servers with VMware Workstation and then for everything you need (vCenter, storage etc.) create VMs on top of ESXi.
Of course, for vCenter use 64bit Windows Server 2K8 or 2K12, as André suggested.--1 person found this helpful
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There is always the VMware online labs, VMware - NEE - Free registration and practise, practise, practise...This is probably the best way to get familiar with most VMware stack if you don't have time and budget to build lab. Once you get comfortable, definitely consider getting your lab...Nested ESXi is a good place to start.