Not all servers are created equal -- some have optical drives, some don't have. Given that, there might be times where you will be needing an alternative way of installing operating systems to that server. In the case of a VMware ESXi 5 hypervisor, the installer has a smaller footprint compared to most operating systems but, nevertheless, without any optical drive on the server the only other alternative is to install via USB.
This is not rocket science. USB installers are in fact a bit common nowadays. We have covered several how to's including the install of Windows 7 via USB. Aside from Windows, almost all flavors of Linux can be installed via USB, although the network install of Linux is the most prefered.
To create a USB installer, you will be needing the latest VMware ESXi ISO image from VMware. It needs a registered account to be able to download the ISO file. Register as it will be worth it.
Aside from the ISO file, you will also be needing the UNetbootin application. You may visit its sourceforge project page here. The current version of UNetbootin as of this writing is 5.81.
With the pre-requisites satisfied, launch UNetbootin. Tick on "Diskimage", select "ISO" on the dropdown (this is the default selection), and browse the location of the downloaded VMware ESXi 5 ISO file. You should have a Window similar to this (see below).
Double check and ensure that the right USB drive is selected. Hit "OK" and watch UNetbootin build the USB installer.
When UNetbootin installs the Bootloader (STEP#3), you will be asked to overwrite a file -- MENU.C32 -- accept that dialog. This is the only interaction that happens during the build. Everything else is automatic.
Upon completion, simply press "Exit". There is no need to reboot.
The only caveat I have encountered on this build is that the USB drive used was formatted NTFS. This doesn't work so early on, you need to format the USB drive with a FAT32 filesystem. This solved a few headaches for me.