We regard a system of left invariant vector fields $\mathcal{X}=\{X_1,\dots,X_k\}$ satisfying the H\"ormander condition and the related Carnot-Carath\'eodory metric on a unimodular Lie group $G$. We define Besov spaces corresponding to the sub-Laplacian $\Delta=\sum X_i^2$ both with positive and negative smoothness. The atomic decomposition of the spaces is given. In consequence we get the distributional characterization of the Hausdorff dimension of Borel subsets with the Haar measure zero.