The efficient utilization of lignin, a pivotal component of lignocellulosic biomass, is crucial for advancing sustainable biorefinery processes. However, optimizing lignin valorization remains challenging due to its intricate structure and susceptibility to undesirable reactions during processing. In this study, we delve into the impact of various pretreatment agents on birch lignin, aiming to enhance its catalytic oxidation and depolymerization under polyoxometalates (POMs) catalysis. Our results reveal that pretreatment with formaldehyde effectively safeguards aryl ether linkages in lignin, leading to a notable increase in aromatic compound yields under POMs catalysis. Furthermore, gel permeation chromatography (GPC) analysis underscores the inhibition of aryl ether linkage hydrolysis upon formaldehyde addition. Gas chromatography–mass spectrometry (GC–MS) analysis demonstrates that formaldehyde pretreatment boosts lignin monomer yield by 2 to 3 times compared to untreated lignin, underscoring the effectiveness of tailored pretreatment strategies. This research underscores the significance of adopting rational pretreatment methods to advance lignin valorization pathways catalyzed by POMs, thereby contributing to the evolution of sustainable biomass conversion technologies.