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Pucon offers a wide range of adventure activities: hiking, horse-back riding, white-water rafting, jungle canopy tours, hot-springs, lava caves, and volcano climbing.
The white-water rafting is among the best in the world. The Pozones hot-springs are the best to try - they offer 5+ natural pools of varying temperature, and the Pozones resort is open until late at night for relaxation after a difficult hike. The Villarica volcano is a great climb if you like mountaineering, but be prepared for a difficult seven-hour day of strenuous climbing.
If you decide to try any of these activities, make sure you use a well-established tour operator. The largest hotels (Hotel Pucon, Antumalal) have tour operators inside their reception area, and, usually, these are the most reliable tour operators. If you walk around town you will see a tour operator in every nook and corner; however, many of these seemingly-official operators will offer cheaper prices but then rip you off. For example, Trancura, a tour operator with a very large and impressive office, offers "natural hotsprings" at a discount price, but then takes you to a man-made jacuzzi in a lodge after you have paid.
Quite true, there are many agencies and even more that say they are agencies, but only sell someone else's services at any cost. The best way to protect yourself from this is to ask around and check equipment (is it clean, dry, in good condition?), facilities (bathrooms, dressing rooms, rest areas?), safety (radio contact with groups), cancellation policies, services and information given. Price of excursion in activities that involve mountains or rivers should not be your first determining factor, THINK TRUSWORTHY SERVICE AND SAFETY.
Beware of recommendations from your lodgers...many guide themselves by which agency pays them a higher commission (2007 examples: La Tetera, Ecole) and not by professionalism, your safety and comfort. The experience of other foreign tourists can also be of great help, but remember that not being able to reach the summit of the Villarrica Volcano is not equivalent to bad service...weather conditions at the moment and YOUR past experience in these conditions make the difference between continuing or turning around.