Note: I'd like to point out that Regex isn't really the most appropriate tool for this job, it's more appropriate to use the File.IO API to check for path validity - for which I'll point to @dtb's answer.
However, in direct answer to your question without debating the merits of other approaches is this:
The regular expression string used to extract C:\Test from C:\Test\Test\Test\Test where you want the [Drive]:\RootFolder from any given path is:
"[a-zA-Z]:\\[^\\]+"
[a-zA-Z] gives you any single character in the character range a-z or A-Z, thus covering upper and lower case.
followed by a :
followed by \ (\ is an escape character so it must be escaped to use it - you escape the character by prefixing it with a \ so where you want \ you put \\ - make sense?)
[^\]+ means the remainder of the string up to but not including the next instance of a \ or any characters after it.
Also, you can use characters 'unescaped' if you wish by preceding the string with an @ symbol outside the quotes, like so:
@"[a-zA-Z]:\[^\]+"