Polytetrafluoroethylene (PTFE) is valued for its low dielectric constant and loss tangent but has low surface free energy (SFE), hindering adhesion to other materials. Our group developed a copolymer gel, poly(2-(diethylamino)ethyl methacrylate-co-dodecyl acrylate) (P(DEAE-co-DA)), with exceptional adhesion to PTFE. Gel sheets were synthesized via photo-radical bulk polymerization, alongside homopolymer gels poly(2-(diethylamino)ethyl methacrylate) (PDEAE) and poly(dodecyl acrylate) (PDA) for comparison. These were assessed using 90° peel tests, contact angle measurements, and oscillatory frequency sweep tests. The 90° peel tests revealed that P(DEAE-co-DA) exhibited 4–6 times higher peel strength than PDEAE and PDA. SFE was highest for PDEAE, followed by P(DEAE-co-DA), PTFE, and PDA. Theoretical adhesive work (Wa) to PTFE was 48.41 mJ/m² for PDEAE, 44.99 mJ/m² for P(DEAE-co-DA), and 36.51 mJ/m² for PDA, suggesting PDEAE’s superior adhesion. However, experimental peel tests showed P(DEAE-co-DA) had the highest peel strength. To explore this discrepancy, oscillatory frequency sweep tests measured storage modulus, loss modulus, Tanδ, relaxation time (τ), and activation energy (Ea). P(DEAE-co-DA) displayed higher Tanδ, shorter τ, and a significantly lower Ea (8.03 kJ/mol) compared to PDEAE (49.7 kJ/mol) and PDA (15.9 kJ/mol). This low Ea enhances chain mobility, enabling side chains to align with the PTFE surface, strengthening van der Waals interactions. The superior peel strength of P(DEAE-co-DA) primarily stems from enhanced viscoelastic energy dissipation, explaining its outstanding adhesion despite a lower theoretical Wa.