Up to 20% of total knee arthroplasty (TKA) patients continue to experience chronic postsurgical pain. Various factors have been identified as potential contributors, including so-called “yellow flags”, encompassing symptoms of depression, anxiety, and catastrophizing, which were examined in this study to assess their predictive value concerning functional outcomes after TKA. Methods: Fifty TKA patients were categorized into high-risk and low-risk groups based on clinical assessment, demographic data, medication, and patient-reported outcome measures (DN4, SF-36, WOMAC, NRS, Fibromyalgia Survey Questionnaire, Pain Catastrophizing Scale, and Hospital Anxiety and Depression Scale). Postoperative outcomes within six months after TKA were then compared. Results: Both groups exhibited significant (p < 0.001) improvements in all WOMAC and NRS subscales, as well as in the physical function, role physical, pain, and energy/fatigue subdomains of the SF-36 after six months, while the high-risk group showed lower WOMAC scores regarding stiffness (19.0 ± 18.3 vs. 27.2 ± 20.7, p < 0.001) and pain (13.5 ± 13.3 vs. 15.1 ± 16.3, p = 0.029). The high-risk group showed significantly worse preoperative DN4 scores (1.8 ± 1.3 vs. 3.0 ± 1.1, p = 0.002) than the low-risk group, which persisted for one day (2.3 ± 1.2 vs. 3.5 ± 1.5, p = 0.005) and six weeks (2.2 ± 1.9 vs. 3.6 ± 2.3, p = 0.041) postoperatively. Conclusions: Our results indicate that pre-existing yellow flags contribute to a more challenging early postoperative phase, underscoring the importance of considering individual patient characteristics and psychological factors to optimize TKA outcomes.