Add-on software packages.
See http://www.pathname.com/fhs/2.2/fhs-3.12.html for details.
Also described at Wikipedia.
Its use dates back at least to the late 1980s, when it was a standard part of System V UNIX. These days, it's also seen in Linux, Solaris (which is SysV), OSX Cygwin, etc. Other BSD unixes (FreeBSD, NetBSD, etc) tend to follow other rules, so you don't usually see BSD systems with an /opt unless they're administered by someone who is more comfortable in other environments.