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In this work, we present the synthesis, characterization, and optical properties of Sr5Si7P2N16:Eu2+, the first tetrahedral (Si,P)–N network in which Si occupies more than 50% of the tetrahedra. While past studies have shown progress with anionic (Si,P)–N networks, the potential of silicon-rich compounds remains untapped. The synthesized compound Sr5Si7P2N16exhibits a unique mixture of substitutional order and positional disorder within its network. The analytical challenges posed by the similarities between Si4+and P5+, along with the network’s disorder, were overcome by combining single-crystal X-ray diffraction and scanning transmission electron microscopy EDX mapping. Low-cost crystallographic calculations provided additional insights into the identification of tetrahedral occupations in mixed networks. Luminescence investigations on Sr5Si7P2N16:Eu2+revealed yellow emission, adding to the known blue, green, and orange emission maxima of Sr–(Si,P)–N networks, highlighting the variability of such compounds.