Poly(L-lactide) electrospun mates have been produced with random and aligned fiber orientation and degrees of crystallinity from 0 up to nearly 50%. These two factors, fiber alignment and degree of crystallinity strongly affect the hydrophobicity of the samples, being this larger for the aligned fiber mats and for the fibers with higher degree of crystallinity. Whereas the first effect can be associated to a 10 decrease in the degree of porosity the second should be related to an increase in fiber stiffness as the observed fiber roughness variations does not show strong differences between the samples. Proliferation of human chondrocytes cultured in monolayer on these substrates is similar in both aligned and non-aligned amorphous mats. Crystallization of the aligned mats, on the other hand, nearly suppresses proliferation and the cells produce higher amounts of aggrecan, characteristic of the extracellular matrix 15 of hyaline cartilage.