High-performance polymers such as poly(ether ether ketone) (PEEK) are appealing as composite components for a wide variety of industrial and medical applications due to their excellent thermomechanical properties. However, conventional PEEK metallization methods can often lead to poor quality control, low deposition rate, and high cost. Cold spray is a promising potential alternative to produce polymer–metal composites rapidly and inexpensively due to its relatively mild operating conditions and high throughput. In this study, we investigated the deposition characteristics of metal–polymer composite feedstock, composed of PEEK powder and copper flake in varying ratios, onto a PEEK substrate. Copper-PEEK powder blends were prepared by both hand-mixing and cryogenic milling (cryomilling), which predominantly creates composite particles with micron-scale copper domains coating PEEK particle surfaces. This process non-monotonically affects the relative dominance and length scales of the multiple contributing deposition mechanisms present in mixed-material cold spray. In low-pressure cold spray, deposits showed significant changes in deposition efficiency and composition as a result of milling, with improvements in these characteristics most dramatic at lower Cu fractions. Deposits of a cryomilled blend of nominally 30 vol.% copper in PEEK exhibited minimal porosity under scanning electron microscopy, complete retention of powder composition, and the highest deposition efficiency among all samples tested. Notably, neither neat PEEK nor neat Cu meaningfully deposited at the same mild conditions as this 30 vol.% Cu blend, indicating a synergistic departure from linear mixing rules driven by the relative balance of local deposition interactions (e.g., hard–soft, soft–soft, etc.). Intentional powder and process design toward optimizing this balance may facilitate cold spray metallization applications.