According to the source code of File.java, pathSeparator is pulled from the char System.getProperty("path.separator", ":").charAt(0). separator, on the other hand, comes from System.getProperty("file.separator", "/").charAt(0).
Because Android is Linux-based, it should always be /. However, I have seen glitches where : has appeared instead (Motorola Droid; see bug report), by using the default value above.
When I code, I always use /... to be honest, I don't think it's necessary to reference the File class (this would mostly be for non-Android work). It's just best to stick to /, I think.
Additionally, according to this answer (pertains to Java, not just Android), / can safely be used on all Java platforms, and it will figure out what it needs to use internally.