Polyether ether ketone (PEEK) is known for its exceptional mechanical properties but has relatively insufficient tribological characteristics. This study seeks to enhance its tribological performance without compromising mechanical properties by fabricating PEEK composites incorporating minimal UHMWPE from 1.0% to 10.0% using hot molding. The hardness, compressive strength, and dry reciprocating friction against bearing steel were evaluated. Results revealed that incorporating just 2.0% UHMWPE into the PEEK matrix significantly reduced the friction coefficient, wear rate, and worn surface roughness by 61%, 89%, and 74%, respectively, compared to pure PEEK, while achieving a notably smooth worn surface. The 2.0% UHMWPE-reinforced PEEK exhibited excellent hardness and compressive strength comparable to pure PEEK, but higher UHMWPE contents decreased these mechanical properties. The UHMWPE proportion of 10.0% resulted in severe adhesive wear, including distinct spalling, plastic deformation, and material accumulation.