Polymer nanocomposites continue to receive considerable attention as multifunctional hybrid materials, with most nanocomposites fabricated by physical dispersion of surface‐functionalized nanoscale objects. In this study, we explore the viability of growing Pd‐containing nanoparticles from Na2PdCl4 in two different polymers: hypercrosslinked polystyrene (HPS) and an aromatic polyimide (PIm). In HPS, single Pd‐containing nanoparticles possessing a relatively narrow size distribution (ca. 1–4 nm) form upon reduction of the divalent PdCl ions. Single nanoparticles with a broad size distribution ranging from ≈2 to 16 nm develop in PIm, which simultaneously undergoes chemical crosslinking during ion reduction. Such hybrid materials hold promise in molecular catalysis and gas separation.