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From San Jose, the best route is to take the Inter-American Highway to the San Ramon exit (about 1 hour) and then continue, following brown volcano signs for Arenal, leaving via Los Angeles. This route is windy and often slow, with large trucks. The whole trip is between 3 and 4 hours. If you are looking for a stopover on the way there or back to San Jose, consider Villa Blanca Cloud Forest Hotel & Spa, which gives the visitor an opportunity to visit a pristine cloud forest without venturing to Monteverde, or the Inn at Coyote Mountain, on a beautiful private nature preserve overlooking the Pacific Ocean with tropical dry forest.
Step-by-step video: Driving instructions from Juan Santamaría int. Airport (SJO) to Arenal Volcano
From any car rental (hire) of your choice, most close to the airport, take the highway into SJ. Stay on the right and get used to the traffic. Once you hit the built up area, stay left (it's a one-way then) and start looking at cross street names. Look for "Calle Central", turn left into it, and it will lead you into HWY 32. The signs are not very good, so go slowly and ignore the horns behind you. You can easily miss that turn. Once you have HWY 32, you're okay. The trip will be around 4 to 5 hours, depending on traffic. There are likely lots of logging trucks on the road.
On the trip down HWY 32 you will pass the Braulio Carrillo National Park and the Rain forest Aerial Tram. Continue driving through Guapiles, Siquirres and Matina. Just before arriving downtown Limon you will pass through a cemetery. Continue on that road for about 1 kilometre and then you will see the sign on your right to Cahuita/Pto. Viejo. Turn here to the right and continue on this road ( HWY # 36) straight ahead, south along the coastline; follow the signs to Cahuita, Puerto Vargas and Puerto Viejo. If you continue driving south, you will end up at Punta Cocles, Punta Uva and Manzanillo National Park. This final stretch of road from Limon onwards can be very rough, so go slow. For the return trip, go again via Guapiles : "El Suerre" is a great place to stay there.
From Guapiles then on to Pto.Viejo (Sarapiqui the "other" Puerto Viejo). The drive onwards then through the hills, San Miguel, Volcan Poas, Varablanca, down to Alajuela is a treat, some stretches reminding of the Austrian or Swiss Alps, complete with Holsteins grazing. This area is worth a few days alone. There is a great (although expensive) lodge in the hills: Peace Lodge
Bonus point of this route: you end up behind the airport (Alajuela) and right at the car rental, without having to cross town again."