I always get this question from people, who are coming for the first time to Rio or just want an advice from a local person, because they just don't want to stay on those regular touristic spots, so I researched some different alternative hotels for those of you, who enjoy to stay on boutique hotels or more exclusive places. My tips are:
Marina All Suites - Top contemporary designers beautifully decorated it.The health club and pool on the roof top has fantastic views. Everything at this boutique hotel is aesthetically pleasing to the eye.
Location: Situated in front of the beach of Leblon south end of Ipanema.
Address: Marina All Suites - Av. Delfim Moreira, 696 Leblon - Rio de Janeiro 22441.000 Phone: 55 (21) 2172-1001
La Maison - is a boutique hotel located at Gavea neighborhood and has only 5 rooms, differently decorated, and the sensation is that you are in a friend house. The only thing to be advised is that they don't accept credicards.
Location: Situated in Gávea a very residential area. Address: Rua Sergio Porto, 58 - Gávea - Rio de Janeiro Phones: 55 -21- 3205-3585 / fax: 55-21-2540-0554 / mobile: 55 -21-7812-5836 / 55 -21- 7812-5837
Casa 32 - If you crave somewhere different to stay in Rio, Casa 32 is really a cool choice. Located in a historical spot called Largo do Boticario, it lies beneath a steep backdrop of Atlantic rain forest not far from the station that leads you to the Christ. Kings Edward VIII and George VI once stayed there as did Le Corbusier, Niemeyer, Portinari and other key Brazilian figures.
Lucio and his family, the owners, recently renovated the house and put it back to its former splendor. Today it's a wonderful mix of modern and antique styles: There are just 2 suites both luxuriously decorated. Location: Cosme Velho Address: Largo do Boticário , 32 - Cosme Velho / 22241-120 - Rio de Janeiro, RJ, Brasil Phone/Fax: +55 21 2265-0943
La Suite - is a sister hotel of La Maison, the owners are the same. La Suite is located in Joatinga has only 7 rooms very well decorated and the views are breath taking. If you are looking for a more secluded spot and with nice views, this is your place. Ps: Does not accept credicards.Location: Joatinga Address:
Rua Jackson de Figueiredo, 501, Joa, Rio de Janeiro Phone:
+55 (21) 24 84 19 62
Relais Solar - located at the hillside streets of Santa Teresa, offers 5 bedrooms, including one bungalow, all the rooms gives you the sensation that you are out of the city, because is surrounded of great vegetation plus the beautiful views of the city. Location: Santa Teresa Address: Ladeiro do Meirelles, 32 Santa Teresa, Rio de Janeiro 20241-340 Phone: +55 (21) 2221 2117

Casa Amarelo - located also at the hillside of Santa Teresa, this pousada was created by Laurent Gelis, and still keeps the nostalgic, old style elevator and original tiles, etc. Everything with a great taste...Location: Santa Teresa Address: Rua Joaquim Murtinho, 569 Phone: +55 21 8886-4314
www.casa-amarelo.com
Also, I found those two sites that gives great tips about those escaped places in Brazil, check www.i-escape.com and www.mrandmrssmith.com