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-Al-27{P-31}-, Al-27{Si-29}-, Si-29{P-31}-, and P-31{Si-29}-REDOR (rotational echo double resonance) NMR spectroscopy as well as P-31{Al-27}- and Si-29{Al-27}-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 Q(P)(2), Q(P)(3), and Q(P)(4) (with the superscript denoting the number of bridging oxygens), the Q(P)(4) units can be safely identified with the help of P-31 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 Q(P)(2) units necessitates an alternative charge compensation scheme for these AlO4 units via formation of Q(P)(4) 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.