The electronic band structure of heavily boron doped diamond was investigated by angle-resolved photoemission spectroscopy on (100)-oriented epilayers. A unique set of Luttinger parameters was deduced from a comparison of the experimental band structure of metallic diamond along the Delta (GammaX) and Sigma(GammaK) high-symmetry directions of the reciprocal space, with theoretical band structure calculations performed both within the local density approximation and by an analytical k·p approach. In this way, we were able to describe the experimental band structure over a large three-dimensional region of the reciprocal space and to estimate hole effective masses in agreement with previous theoretical and experimental papers.