I haven't taken 64 all the way across Tennessee, but I have been on a good part of the western half of the state. It passes primarily through Small Town, Tennessee and if that's the type of scenery you want you will enjoy it. It's pretty much one small to mid-sized town after another. Adamsville, TN is the former home or Sheriff Buford Pusser of Walking Tall fame. Just east of Adamsville in Crump there is an AH-1 Cobra helicopter on static display that always needs a little company. Pulaski, TN to the east has the dubious honor of being the birthplace of the KKK. Around Sewanee it starts getting hilly and very pretty. Sewanee has a natural stone arch bridge of some fame.
Hwy 64 merges with I-24 at Monteagle and I'd recommend picking up Highway 41 there. Follow it to Jasper, TN and you can pick up 64 again (41 & 64 are the same highway) around Nickajack Lake into Chattanooga. I haven't been on it east of Chattanooga so I don't know what it's like.
All in all it's an easy, quiet ride through some scenic countryside. Nothing twisty or technical or mountainous or difficult. Just laid-back and easy.
Scott Craig - Nashville, TN
Red '06 Suzuki DL650 - Red '07 Honda VFR800 - My Bike Page