Just finished riding a couple thousand kms around NSW. Highlights were:

Old Pacific Hwy between Hornsby and Central Coast Hwy; and

Macquarie Pass between Albion Park and Robertson. 

Not only are these roads nice and twisty, but the road surface was far better than I would have ever expected. 

 

Im sure others will have good roads to recommend riding on. 

Some fantastic roads up the snow country during summer.

The mother of all bike roads in NSW is Putty

Snowy Mountains Hwy - Tumut to Adaminaby, or any of the roads around that area.

Tumut to Tumbarumba via Cabramurra is a brilliant road. I live in Wollongong and my Sunday ride is up the Macquarie pass and back down the Jamberoo mountain road for a beer at the Jamberoo pub. its a hard life eh?

Yep - Thredbo to Khancoban is awesome too! Will probably do it again this year on the Snow Ride.

As 92Fatboy say's, The Putty Road
.

The best road is the bit of bitumen at the end of the driveway at work.
Its been the start of many a good ride.

+1 for Putty Rd.

Bells Line to Lithgow. Bylong Valley Way. West Head (great but way too short). Turandale Rd/Hill End Rd between Orange and Mudgee. Wollombi. Moss Vale Rd through Kangaroo Valley.

Always looking for new roads...

Bermagui to Tathra Rd, then to Bega & up Princess Hwy to Snowy Mountains Hwy & just keep riding all great roads & not too much traffic on the Gui to Tathra Rd & some nice beach's along there.

 

What about roads north of city? Central Coast and Hunter. Sick of riding the same old routes.

G'day Krash,, Just had a ride ,(yesterday), around the Bermagui and Tathra area with a few mates. There is a Poker run , called the Tuross Heads One Tree Poker run on 25th October 2014. Takes in this area , plus a lot more country roads .. Great excuse to check out that part of NSW. I'll post the ride up in the ride thread soon .

Thunderbolt Way from Gloucester to Uralla is pretty awesome and hardly any Traffic.

Anyone know if Comboyne Rd (southwest of Port Macquarie) is sealed and worth a look?

What's the Kyogle Road like from Casino through to Murwillumbah? It looks very interesting on the map.

Maquarie Pass is a nice road since they resurfaced it, but there are too many trucks on that road these days, as for Jamberoo Pass that is ok but its very narrow and you have to watch the cars also bikes cutting the corners. Roads out around the back of Picton, Oaks, Oakdale and up to Burragarang look out are nice and I mean nice in the view and there is not much traffic around most days.

The Oxley Highway west of Port Mac 

From Cootamundra to Harden then to Rugby, Boorowa then into Crookwell is a nice twisty ride, can be a little bumpy in some sections but worth it. Came home thru Goulbourn and you can detour off the Hume and go the tourist road which goes thru Bundanoon - very nice and back down Macquarie Pass.
Really any road where the aren't as many cars is great in my books.
Just did a 4 day ride up the Putty to Denman, then thru the Bylong Valley to Rylestone and Kandos, back up to Wellington, then out to Parkes and thru Young and Forbes to Cootamundra - absolutely beautiful, wanted to turn around and do it in reverse.

DocGreen

Canberra to Batemans bay via Braidwood

Cronulla to Kurnell then back down to Wollongong via the Royal National Park...enter the Park via Princes Highway at Loftus

The Oxley Hwy up to Gingers Creek from Wauchpe is about 110, 120ks good surface 300+ corners according to the tee shirts sold at Gingers Creek.