In order to reveal fundamental tribological mechanisms in polymer/steel sliding pairs, the pin-on-flat configuration of classical macroscopic tribotests was transferred into a high-resolution tribometer designed for scratch tests. Experiments were performed with a polyetheretherketone (PEEK) pin sliding on a steel disk in straight unidirectional movement mode. The surface morphology was monitored by interrupting the tests every 10,000 sliding strokes. The evolving surface morphology of PEEK was correlated with the transfer layer formed on steel counter surface. Scratching grooves in the PEEK surface were induced by asperities at the counter steel surface covered with transfer layers. Transfer layers were composed of lumpy polymer material accompanied by fine wear debris in areas of lower roughness. These smooth areas limit the penetration of large asperities and distinguish the scratching mechanism in macroscopic sliding from typical single-asperity scratching tests. The results reveal the mechanisms leading to inhomogeneity in the transfer layers as consequence of the asperity distribution.