Tourism in the villages is more laid back than Amalfi. Here you will find more low modest hotels and rental apartments and more B&Bs than in Amalfi where chic Luxury hotels abound. And although Amalfi has some great hiking with its Sentiero degli Dei (Path of the Gods) high above the towns and villages of the Coast Road, the Cinque Terre has its paths connecting each village... and they are wonderful walks with gorgeous views. Keep in mind however, that these walking paths--although well paved and often wide promenades--have lots of people walking them in the high season. They are also rugged in terms of changes in altitudes--lots of ups and downs, so you'd better be in good shape. I wouldn't recommend Cinque Terre for seniors or people with heart or breathing difficulties. In Amalfi, the Path of the Gods is for more serious hikers with some easier parts paths mixed in all throughout the peninsula, but most of the tourists are going to the chic towns of Positano and Amalfi Town--the place is very touristy.
When visiting Italy in early spring or fall, you might have better weather in the south, but by American standards, the weather is still warm enough to enjoy a slightly off-season trip to Cinque Terre. In later October the rains and some winds start to come, so plan your trip later in the month. If you want to swim in the sea, plan your trip at the shoulder of the high season. If you don't mind more crowds, humidity and heat, plan your trip in summer. Personally, I would also squeeze in some time in Portovenere and perhaps have a water taxi drop me off on the Isola Palmeria--a national park with wonderful naturalized beaches that look back at the the town. There are hiking tails on the Island with amazing views and lots of nature to enjoy.
Of course, you might not want to hike between all of the towns... You will want to take the trains also.
The Cinque Terre trains connect six stops: La Spezia (just down the coast to the east of Cinque Terre, it's where you would make connections to other major Italian cities) the official "Five Lands" of Riomaggiore, Manarola, Corniglia, Vernazza, and Monterosso, and the town of Levanto. If you're coming from elsewhere in Italy, you would have to connect to either Florence, Milan, or Venice and then move on to La Spezia to connect with the Cinque Terre train system.From La Spezia to Riomaggiore is about 10 minutes, and then roughly 5 minutes between each town thereafter. The trains run an irregular, perhaps some would say unreliable schedule, but you can usually catch a train every hour or so. You can also travel between towns by water taxi which leave every hour or so.
Bottom line... Cinque Terre is a bit less touristy than the Amalfi Coast, has less of that chic element and more of the backpacker feel, and is more suited to serious hikers and walkers looking for a more intimate getaway.
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