Romania still has a lot to offer to tourists willing to do a bit of independent travel, however, it is not like the Borat film I had imagined. Romania is as advanced as anywhere else in Europe in many respects. There is no problem at all finding people who speak English, getting mobile reception, cash from local cash machines and so on. About half of the taxi drivers do their best to rip you off, but not much more so than in the Baltics. Also, transport is seriously limited. No motorways and trains are often cancelled or run at a snails pace.
I spent most of my time in Brasov which is a pretty good place to base yourself for hiking in the Carpathians. Brasov itself is a nice enough Medieval city with lots of restaurants, accommodation and bars. There is an absurd proportion of pizza restaurants. Two other things that struck me were the sheer number of taxis and pensiunnes (guest houses) and that Romanian is reasonably easy to understand when it is written down.
Walking from Brasov
This is what I recommend you do if you want to go hiking in the Sourthern Carpathians with Brasov as a base.
Day 1: Walk to Poiana Brasov. There are two routes that link up. You can either walk straight out of Brasov, up through the Shei district and into the forest or get the cable car to the Hollywood sign and walk from there. I doubt there's much difference, but I've only done the former. In Poiana Brasov you can stay at the mountain refuge ('Cabana') Postavaru, which is massive with loads of facilities, a nice bar a good food.
Day 2: Walk to Timisu de Sus. I didn't do this but the surrounding area looked excellent. I don't know anywhere specific to stay there but there are definitely several hotels down there. A few km up the road is Dimbu Morii, where unfortunately the main refuge is now derelict but there's loads of other options and places to camp.
Day 3: Walk to Piatra Mare Cabana. This is very small but in a stunning location. There's a variety of scenes along the way from canyons to medows, pastures and a small waterfall (Cascade Tamina). They only have one dormitry at the cabana and when I was there the only food they could offer was 'some soup from beans' but they're nice people. Anna Maria ('Mary') speaks English.
Day 4: Walk down to Dimbu Morii. This features the 7 steps water fall, which is good fun. From hear you can walk about 3km back into Brasov and get the 17 bus back into town.
If you've got more time you could head off further into the Carpathians from Piatra Mare, but I don't know anything about this. It looked excellent from the cabana, and in theory you could walk to Poland with little interuption.
If you need a taxi driver in the Brasov area or need a Brasov to Bucharest transfer I recommend Gabi Rosu. He speaks very good English and will not rip you off. His number in Romania is 0721 123360.