Air filled porosity (AFP) appears as the best measure to determine the available porosity in a composting material or, in general, in an organic matrix. Several methodologies, including theoretical and empirical approaches have been developed to estimate AFP. Among them, air pycnometry has been considered the most suitable and accurate technique to obtain reliable measures of AFP. In this review, the published methodologies to determine AFP by air pycnometry are explained in detail, and the main advantages and disadvantages of such methodologies are discussed. Also, a massive sampling of several organic wastes and mixtures intended for composting has been characterized by air pycnometry, and the theoretical and empirical correlations proposed in literature are compared in terms of accuracy in AFP measurement. Results obtained show that some theoretical correlations are suitable for estimating AFP in the majority of organic wastes studied. However, some waste samples need an experimental determination to obtain a realistic value of AFP.