This study aims to reveal the effects of flexible chain lengths on rosin-based epoxy resin’s properties. Two rosin-based epoxy monomers with varying chain lengths were synthesized: AR-EGDE (derived from ethylene glycol diglycidyl ether-modified acrylic acid rosin) and ARE (derived from acrylic acid rosin and epichlorohydrin). Diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) with different flexible chain lengths were used as curing agents. The adhesion, impact, pencil hardness, flexibility, water and heat resistance, and weatherability of the epoxy resins were systematically examined. It was found that when the flexible chains of rosin-based epoxy monomers were grown from ARE to AR-EGDE, due to the increased space of rosin-based fused rings, the toughness, adhesion, and water resistance of the rosin-based epoxy resins were enhanced, while the pencil hardness and heat resistance decreased. However, when the flexible chains of curing agents were lengthened, the resin’s performance did not change significantly because the space between the fused rings changed little. This indicates that the properties of the rosin-based resins can only be altered when the introduced flexible chain increases the space between the fused rings. The study also compared rosin-based resins to E20, a commercial petroleum-based epoxy of the bisphenol A type. The rosin-based resins demonstrated superior adhesion, water resistance, and weatherability compared to the E20 resins, indicating the remarkable durability of the rosin-based resin.