Castor is an important non-edible oilseed crop used in the production of high-quality bio-oil. In this process, the leftover tissues rich in cellulose, hemicellulose and lignin are regarded as by-products and remain underutilized. Lignin is a crucial recalcitrance component, and its composition and structure strongly limit the high-value utilization of raw materials, but there is a lack of detailed studies relating to castor lignin chemistry. In this study, lignins were isolated from various parts of the castor plant, namely, stalk, root, leaf, petiole, seed endocarp and epicarp, using the dilute HCl/dioxane method, and the structural features of the as-obtained six lignins were investigated. The analyses indicated that endocarp lignin contained catechyl (C), guaiacyl (G) and syringyl (S) units, with a predominance of C unit [C/(G+S) = 6.9:1], in which the coexisted C-lignin and G/S-lignin could be disassembled completely. The isolated dioxane lignin (DL) from endocarp had a high abundance of benzodioxane linkages (85%) and a low level of β-β linkages (15%). The other lignins were enriched in G and S units with moderate amounts of β-O-4 and β-β linkages, being significantly different from endocarp lignin. Moreover, onlyp-coumarate (pCA) incorporated into the epicarp lignin was observed, with higher relative content, being rarely reported in previous studies. The catalytic depolymerization of isolated DL generated 1.4–35.6 wt% of aromatic monomers, among which DL from endocarp and epicarp have high yields and excellent selectivity. This work highlights the differences in lignins from various parts of the castor plant, providing a solid theory for the high-value utilization of the whole castor plant.