Near infrared photoluminescent porous silicon nanocrystals(ncSi)‐polyhedral oligomeric silsesquioxanes (POSS) polymer composites are synthesized using a combination of thermal hydrosilylation and polymerization between Vinyl‐POSS and hydrogen‐terminated silicon nanocrystals (ncSi:H). The synthesized materials are characterized by IR, powder X‐ray diffraction and solid‐state nuclear magnetic resonance (NMR) (¹³C and ²⁹Si). The results demonstrate that the hydrosilylation–polymerization reaction proceeded to create chemically crosslinked Vinyl‐POSS‐ncSi composites in which the integrity of the POSS cages is maintained intact. Scanning electron microscope (SEM) results demonstrate that morphology of these materials depends on the weight ratio of ncSi:H to Vinyl‐POSS. Brunauer–Emmett–Teller surface area analyses establish that the composites have high surface areas ranging from 290.5 to 1047.2 m² g⁻¹ and pore volumes from 0.64 to 1.17 cm³ g⁻¹. The pore sizes range from 6.08 to 3.54 nm and are dependent on the weight ratio of Vinyl‐POSS to ncSi:H. Photoluminescence spectroscopy shows that the absolute quantum yield of the nanocomposites is not affected by the weight ratio of ncSi:H to Vinyl‐POSS. Thermal gravimetric analysis results show that the POSS polymer composites with ncSi have lower thermal stability in nitrogen atmosphere as compared with the pure Vinyl‐POSS polymer. It is envisioned that future applications for these composites will likely be found in the fields of advanced materials, gas adsorption media, and biomedicine.