Three-dimensional printing polyetheretherketone (PEEK) provides a new choice for dental prostheses, while its appropriate bonding procedure and adhesive performance are still unclear. This study aimed to investigate the adhesive performance of printed polyetheretherketone (PEEK) after acid etching to veneering resin. In total, 182 PEEK specimens (including 91 printed and 91 milled specimens) were distributed to 14 subgroups (n = 13/subgroup), according to the manufacturing process and surface treatment. The specimens were polished and etched with sulfuric acid for 0, 5, 30, 60, 90, 120, and 300 s, respectively. Two specimens in each subgroup were observed under a scanning electron microscope (SEM) for surface and cross-section morphology separately. Then, the specimens were treated with a bonding primer, and one specimen in each subgroup was prepared for cross-sectional observation under SEM. The residual 10 specimens of each subgroup bonded with veneering resin were tested with the shear bond strength tests (SBS) and failure modes analysis. Statistical analysis was performed by one-way ANOVA followed by the SNK-q post hoc test (p < 0.05). The etched pores on the PEEK surface were broadened and deepened under SEM over time. Printed PEEK etched for 30 s obtained the best SBS-to-veneering-resin ratio (27.90 ± 3.48 MPa) among the printed subgroups (p < 0.05) and had no statistical differences compared with milled PEEK etched for 30 s. The SBS of the milled subgroups etched from 5 to 120 s were over 29 MPa without significant between-group statistical differences. Hence, printed PEEK can be coarsened effectively by 30 s of sulfuric acid etching. The adhesion efficacy of printed PEEK to veneering resin was qualified for clinical requirements of polymer-based fixed dentures.