Hi, I crossed last year via the Ukrainian city of Kharkiv. No problem whatsoever. Kharkiv is a beautiful city. To get there, you can either follow the highway (boring dead straight), or go via country roads (very interesting but lots of potholes). Most friendly people everywhere.
The Belgorod border post is 10km away from Kharkiv. Get there before 7:00AM and wait of the border to open, or be prepared to need more than 5 hours going through insane bureaucracy and forms between 2 different offices which close at radom with Russian officers disappearing and reappearing randomly.
Caution: Belgorod is the ONLY border post which will allow non-Ukrainians or Russians into (or out of) Russia in that part of Ukraine. I tried several ones all the way 250km South of Kharkiv and was pushed back everywhere.
Also, I could not see any insurance office at Belgorod last year. You get fined driving without insurance in Russia (and it is a real hassle to get in trouble). Get it at first city unless you can now get it a the Belgorod border.
Safe travel.
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