Pendant groups in acrylic adhesive polymers (Ads) have a profound influence on adhesive and cohesive properties and additionally on encapsulant application. However, a systematic investigation to assess the impact of the pendant groups' length and bulkiness is rare, and there is not even a single report on applying Ads as interfacial adhesion promotors and encapsulation materials simultaneously. Herein, we have developed a series of multifunctional methacrylic polymers, namely, R-co-Ads, with varying pendant length and bulkiness (R = methyl (C1), ethyl (C2), propyl (C3), butyl (C4), pentyl (C5), hexyl (C6), isobutyl (iC4), and 2-ethylhexyl (2EH)). The adhesion-related experimental results reveal that R-co-Ads have high transparency, strong adhesion strength to the various contact surfaces, and a fast cure speed. In particular, C1-co-Ad shows a superior adhesion performance with an improved cross-cut index of 4B and a shear bonding strength of 1.56 MPa. We also have adopted C1-co-Ad for encapsulation of various emerging optoelectronic applications (e.g., perovskite solar cell-, charge transport-, and conductivity-related characteristics), demonstrating its excellent edge encapsulant served to improve the device stability against ambient air conditions. Our study establishes the structure-adhesion-surface relationships, advancing the better design of adhesives and encapsulants for various research fields.