β-cyclodextrin (β-CD) has the characteristics of safety, non-toxicity, and a wide range of sources. It can be used in improving surface activity. However, due to the limitation of molecular polarity and solubility, its surface activity and emulsification ability are weak. Therefore, it is necessary to improve adsorption capacity on phase interface by hydrophobic modification. In this article, dodecenyl succinic-β-cyclodextrin (DDS-β-CD) with different substitution degree was prepared by esterification of β-CD with dodecenyl succinic anhydride (DDSA) as the esterifying agent. The product was characterized by FT-IR, 1 H NMR, SEM, and TGA, respectively. Results showed that DDS was successfully introduced into β-CD. Both the degree of substitution (DS) and productivity (P) increased with the addition of DDSA and can reach 0.283 and 85.8%, respectively, when the molar ratio of DDSA to β-CD was 3:1. The modified cyclodextrin showed lower surface tension and higher foaming ability. Compared with octenyl succinic-β-cyclodextrin (OS-β-CD), it was found that the length of hydrophobic segment had a significant effect on the surface tension. Due to its unique properties, it can be used as a good emulsifier for oil-in-water emulsions and a host material for lavender flavor.