In this contribution we present a detailed study of the effect of the addition of small to intermediate amounts of P2O5 (up to 7.5 mol %) on the network organization of metaluminous sodium aluminosilicate glasses employing a range of advanced solid state NMR methodologies. The combined results from MAS, MQMAS (multiple quantum MAS), or MAT (magic angle turning) NMR spectroscopy and a variety of dipolar based NMR experiments-27Al{31P}-, 27Al{29Si}-, 29Si{31P}-, and 31P{29Si}-REDOR (rotational echo double resonance) NMR spectroscopy as well as 31P{27Al}- and 29Si{27Al}-REAPDOR (rotational echo adiabatic passage double resonance) NMR-allow for a detailed analysis of the network organization adopted by these glasses. Phosphate is found as QP2, QP3, and QP4 (with the superscript denoting the number of bridging oxygens), the QP4 units can be safely identified with the help of 31P MAT NMR experiments. Al exclusively adopts a 4-fold coordination. The withdrawal of a fraction of the sodium cations from AlO4 units that is needed for charge compensation of the QP2 units necessitates an alternative charge compensation scheme for these AlO4 units via formation of QP4 units or oxygen triclusters. The dipolar NMR experiments suggest a strong preference of P for Al with an average value of ca. 2.4 P-O-Al connections per phosphate tetrahedron. P is thus mainly integrated into the network via P-O-Al bonding, the formation of Si-O-P bonding plays only a minor role.