Postcollisional magmatism is widely distributed in southern Sinai, the extreme northern part of the Neoproterozoic Arabian-Nubian Shield. This article deals with mineral and whole-rock chemistry of postcollisional syenogranites and associated volcanic rocks from three localities in southern Sinai: Iqna Sharay’a, Rusis-Rutig, and Um Shuki–Abu Khusheib. The studied volcanic rocks have compositions between rhyolites and dacites with minor andesite. Thewholerock chemical compositions of the investigated rock types togetherwith the biotite chemistry are consistent with high-K calc-alkaline and alkaline/peralkaline magma. The studied syenogranites and most volcanic rocks are more akin to anorogenic alkaline within-plate environments. Only a few samples of Um Shuki–Abu Khusheib volcanic rocks display some characteristics of orogenic arc-type environments. The high-K calc-alkaline to alkaline affinity and the relative enrichments in large ion lithophile elements (especially K, Rb, and Ba) and light rare earth elements together with a significant negative Eu anomaly imply that the studied granites and volcanic rocks were generated by partial melting of lower to middle crustal materials accompanied by the underplated mafic magma produced in the lithospheric mantle (convective diffusion). This convective diffusion describes a specific scenario of active chemical interaction between mafic and silicic magmas in order to explain formation of voluminous high-K calc-alkaline and alkaline/peralkaline magmatismin postcollisional tectonic environments. The enhanced temperatures of A-type silicicmagmas ofmore than 10007C suggest that magma generation could occur even at the depth of the uppermost lithospheric mantle.