Vegetable-oil-based polyurethane has become a promising sustainable candidate for controlled-release fertilizer based on green chemistry. The purpose of this study was to prepare a series of coatings from selective feedstocks including five vegetable oils with a high saturation degree, mono-unsaturation degree, or poly-unsaturation degree, considering that vegetable oil fatty acids played a key role in the synthesis of polyol and polyurethane. The effect of the type and proportion of fatty acids on the physicochemical properties, microstructure, and macro-properties of vegetable-oil-derived polyols and their resulting coatings was characterized and discussed. The position and number of the hydroxy groups were determined by the type and proportion of fatty acid, and polyol from linseed oil with a high poly-unsaturation degree and three carbon–carbon double bonds had a high hydroxyl value and functionality, whereas polyol from palm oil with a high saturation degree possessed the lowest hydroxyl value and functionality. The resultant coating from linseed-oil-based polyol had a good cross-linking density, and the nitrogen release longevity of coated urea was 56 days at a coating percentage of 3%, and its nitrogen use efficiency was increased by 27.15% compared with conventional urea. Although the palm-oil-based coating had good hydrophobicity, its coated urea was not ideal. Overall, this study has enriched theories of bio-based polyurethane coatings for controlled-release fertilizers; using vegetable oil with a poly-unsaturation degree, it is easy to obtain an excellent coating for controlled-release fertilizer, and this will help provide economic and environmental benefits.