I think Multics introduced the and presented it at the 1965 Fall Joint Computer Conference. (The reference is one of the papers from that conference, describing the filesystem.) Unix of course also has an hierarchical filesystem, which it seems to have inherited from Multics.
The says: Unix also popularized the hierarchical file system with arbitrarily nested subdirectories, originally introduced by Multics. Other common operating systems of the era had ways to divide a storage device into multiple directories or sections, but they had a fixed number of levels, often only one level. Several major proprietary operating systems eventually added recursive subdirectory capabilities also patterned after Multics. DEC's RSX-11M's 'group, user' hierarchy evolved into VMS directories, CP/M's volumes evolved into MS-DOS 2.0+ subdirectories, and HP's MPE group.account hierarchy and IBM's SSP and OS/400 library systems were folded into broader POSIX file systems.