Sodium aluminophosphosilicate gels and glasses along the composition line (Na2O)x–[(AlPO4)0.5(SiO2)0.5]1−x were synthesized via the sol-gel process using sodium acetate, aluminium lactate, phosphoric acid and tetraethyl orthosilicate (TEOS) as precursors. The structural evolution from solution to gel and to the final glass was monitored by 27Al, 31P, 29Si and 23Na magic-angle spinning (MAS) NMR. In the solution state aluminium forms a mixture of octahedral coordinated complexes coordinated to lactate, water and phosphate units with varying degrees of polymerization. With increasing temperature up to about 150 °C the lactate ligands are successively replaced by phosphate, resulting in an increased extent of Al–O–P linking. Annealing the xerogel at 400 °C results in a glassy network containing mostly four-coordinated Al species (Al(IV)), in addition to small concentrations of Al(V) and Al(VI). While the distribution of Al coordination numbers remains constant, the compositional trend of the 27Al chemical shift indicates a gradual replacement of Al–O–P linkages by Al–O–Si linkages with increasing sodium content. This conclusion is confirmed by 27Al{31P} Rotational Echo Double Resonance (REDOR) experiments, which reveal a reduction in the number of Al–O–P linkages. Concomitantly, the interaction of Na with the phosphate species is successively increased as indicated by 31P chemical shift trends and 31P{23Na} REDOR results. The results illustrate that the network segregation found in pure AlPO4–SiO2 sol-gel glasses can be overcome, at least partially, by introduction of the network modifier Na2O.