Comprehension of short- and medium-range order of phosphate glasses is a topic of interest, due to the close relation between network structure and mechanical, thermal, and optical properties. In this work, the short-range structure of glasses (1 -x)Ca(PO3)(2)(.)xAl(PO3)(3) with 0 less than or equal to x less than or equal to 0.47 was studied using solid-state nuclear magnetic resonance spectroscopy, Raman spectroscopy, density measurements, and differential scanning calorimetry. The bonding between a network modifier species, Al, and the network forming phosphate groups was probed using high-resolution nuclear magnetic resonance spectroscopy of Al-27 and P-31. Changes in the compositional behavior of the density, glass transition temperature, PO2 symmetric vibrations, and A coordination number were verified at around x = 0.30. P-31 NMR spectra show the presence of phosphorus in Q(2) sites with nonbridging oxygens (NBOs) coordinated by Ca ions and also Q(2) sites with one NBC coordinated by Al (namely, Q(2)(1Al)). The chances in the properties as a function of x can be understood by considering the mean coordination number measured for Al and the formation of only Q(2) and Q(2)(1Al) species. It is possible to calculate that a network formed only by Q(2)(1Al) phosphates can just exist up to the upper limit of x = 0.48. Above this value, Q(2)(2Al) species should appear, imposing a major reorganization of the network. Above x = 0.30 the network undergoes a progressive reorganization to incorporate Al ions, maintaining the condition that only Q(2)(1Al) species are formed. These observations support the idea that bonding principles for cationic species inferred originally in binary phosphate glasses can also be extended to ternary systems.