Poly(L-lactic acid) (PLLA) and poly(ethylene oxide) (PEO) blends were prepared by mechanical mixture and fusion of homopolymers. Samples were submitted to in vitro degradation tests (immersion in a phosphate buffer solution with pH = 7.4 at 37 °C). Independently of the blend composition, PEO was dissolved after 14 days of immersion. As expected, after immersion, scanning electron microscopy showed that the blends were porous, contrary to the samples, which were not immersed in the buffer solution. Phase separation was not evident. Using differential scanning calorimetry, the melting points (Tm) of both PLLA and PEO crystalline fractions were observed and remained practically constant, indicating no miscibility. Thermogravimetry showed that the temperature where the main mass loss stage starts (Tonset), depended on the blend composition and period of immersion in the buffer. The blends and the PLLA homopolymer were implanted in defects produced in the tibias of rats. The blends were as biocompatible as the PLLA.