This article investigates the capital structure determination of firms listed on the Athens Stock Exchange, using both cross-sectional and nonparametric statistics. The data set is mainly composed of balance sheet data for 259 firms over a 9-year period from 1998 to 2006, excluding firms from the banking, finance, real estate and insurance sectors. The first part of the study assesses the extent to which leverage depends upon a broader set of capital structure determinants, while the latter provides evidence that capital structure varies significantly across a series of firm classifications. The results document empirical regularities with respect to alternative measures of debt that are consistent with existing theories and, in particular, reasonably support the pecking order hypothesis. Overall, this study tries to shed more light on corporate financing behaviour in a way to loosen the capital structure puzzle.