Porous-silica low-dielectric-constant (low-k) films were prepared using a sol-gel method based on the self-assembly of surfactant templates. No change in the refractive index at 633 nm nor in the infrared-absorption intensities of C–H and O–H stretching vibrations at around 2900 and 3400 cm-1 of porous-silica low-k films were observed after annealing at each temperature from 523 to 723 K. On the other hand, the Young’s elastic modulus and hardness increased with the increase of annealing temperature. The structure in the complex dielectric function of porous-silica low-k films observed in between 1000 and 1400 cm-1 is assigned as the asymmetric stretching vibration mode of the Si–O–Si bond. By applying the effective-medium theory by Bruggeman to the experimental results from infrared spectroscopic ellipsometry, we analyzed the skeletal silica structures. The peak positions of transverse (ωTO) and longitudinal (ωLO) vibration modes for Si–O–Si network in the silica skeleton of porous-silica films changed from 1061 to 1068 cm-1 and from 1219 to 1232 cm-1, respectively, with the annealing temperature. It is shown that the ωLO2/ωTO2 of skeletal silica correlates with Young’s elastic modulus of porous-silica low-k films.