When opening a video file over a samba share I get VLC is unable to open the MRL 'smb://azezal@192.168.1.5/media/cam/2015-05-15_10-00.avi' and it also doesn't open in kaffeine, whereas in gnome or xfce the video files open fine. Reproducible: Always
What happens if you try to use kio_client to copy this file to a different place? Note that VLC probably does not use KIO, so if it is unable to open it, you would have to report this to VLC developers.
If you can provide the information requested in comment #1, please add it.
It seems to work when using kioclient
Should be resolved now with kio-fuse.