Success... I got it working on Debian based SolydX (XFCE). Libre Office Version 126.96.36.199 (Build ID: 400m0(Build:3)).
Firstly I had to install gvfs-fuse (as it was not installed by default), reboot and navigated to the samba shares from Thunar
and opened a .docx file in Libre Office and it worked just fine.
Now I have(wich i did not have before):
mount | grep gvfs
gvfs-fuse-daemon on /home/<user>/.gvfs type fuse.gvfs-fuse-daemon (rw,nosuid,nodev,relatime,user_id=1000,group_id=1000)
So it mounts into .gvfs