Yes, this marks the first time that the Tu-95 and Tu-160 have seen combat. Judging from footage from the ministry of defense, it looks like the Tu-160s were using new Kh-101s, while the Tu-95MS seem to have fired Kh-555 cruise missiles (their bomb bay being too small for the new missile and only test aircraft having been updated with under-wing pylons). I would guess that the Tu-22M3s have been dropping lots of conventional bombs...
Additionally, there have been reports of Kalibr cruise missiles being launch from one of the new Kilo class SSKs in the Mediterranean, while Putin has ordered that Russian ships in the area operate with the French carrier "as allies."
It is also planned that an aditional 8 Su-34s and 4 Su-27SM fighters join the airstrikes, based out of Russia.
Detailed summary from the Russian Ministry of Defense:
http://eng.mil.ru/en/news_page/country/more.htm?id=12066124@egNews