The synthesis and coordination chemistry of 4-pyridinemethylene end-capped MeO-PEG (LPy) to Pd(II) was investigated. The PEG-based macroligand LPy was straightforwardly synthesized by pyridine end-functionalization of PEG monomethyl ether and employed to stabilize Pd(II) in a neutral (1a) and bis-cationic (2a) macrocomplex, characterized by a LPy to Pd molar ratio of 2 and 4, respectively. The homogeneous distribution of the Pd-NPs in 2b exerted a significant stabilizing effect on the poly(ether) chain of LPy against its oxidative thermal degradation. From a screening of the Pd(II)- and Pd-NP-based catalysts in the aerobic oxidation of unsaturated alcohols in water emerged 2b as the most stable catalyst, showing TOF-values up to 200-h and high chemoselectivity even for prolonged reaction times.