Yes, it can on Windows, both via psqlODBC and Npgsql, when you find out which .net runtime version your Excel version uses.
On Mac, it is more interesting; there's only ODBC, Microsoft doesn't support the same psqlODBC you can use in Windows and you have to purchase one of the supported commercial ODBC drivers.
I used to work at big hospital that had a home-grown 'reporting system' built with Excel, data connections to an SQL Server database, and a series of pivot tables. Every morning from 8-9am the whole network would slow as people opened their spreadsheet and it basically did a `select * from a_rather_large_view` - tens of gigabytes flying around (this was in the mid 2000s.)
There was resistance after a data warehouse (BO) was introduced because pivot tables were so flexible and well-understood.