Infrared vibrations of as-deposited and annealed semiconducting boron carbide thin films were investigated by midinfrared spectroscopic ellipsometry. The strong boron-hydrogen resonance at ∼2560 cm−1 in as-deposited films reveals considerable hydrogen incorporation during plasma-enhanced chemical vapor deposition. Extended annealing at 600 °C caused significant reduction in film thickness, substantial reduction of boron-hydrogen bond resonance absorption, and development of distinct blue-shifted boron-carbon and icosahedral vibration mode resonances. Our findings suggest that annealing results in substantial loss of hydrogen and in development of icosahedral structure, accompanied by strain relaxation and densification.