All of Vermont is picturesque. Really. It's Eden in the summer time (and you should plan on coming between mid-July and late August for guaranteed nice cycling weather).
That said, if he isn't a cyclist, I'm not sure I'd go to the Northeast Kingdom. It's probably the most rural part of the state. Not much for him to do.
I'd steer you more towards Waitsfield/Warren/Stowe area. There's still nice cycling there (although it will be considerably hillier) but there is more to do off the bike and it's within 45 min of Montpelier (state capital, cute hippie town) and Burlington (largest city). Or you could stay in Middlebury, where there are a couple of cute B&Bs/inns and plenty of nice cycling around, also about 45 min from Burlington. Alternately, I'd go further south and maybe stay in Woodstock, which is pretty touristy but very cute and there's stuff to do for non-cyclists, and lots of pretty cycling/other stuff to do around Quechee/Norwich/Hanover area which is within riding/driving distance.
Oh -- if you do come to the northern part of the state, you should do a day in the Champlain Islands. It's quite flat, but outrageously pretty and the roads either have lovely wide shoulders or are so quiet that you don't have to worry.



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