When in Enhanced mode, the kernel of Windows 3.1 was 32-bit even though a normal blank install of Windows 3.1 could only run 16-bit software. However, Win32s can be used for running specifically designed 32-bit software on Windows 3.1. I remember that on Windows for Workgroups 3.11 there are even options for 32-bit file access and 32-bit disk access.
I did read that it was written as 16-bit Windows 3.1 vs 32-bit Windows 95 in the mid-1990s but that wasn't true at all.