Solid catalysts, Li-Al layered double hydroxides (Li-Al LDHs), were prepared to catalyze the transesterification of soybean oil (SBO) with ethylene glycol. To improve catalytic activity, the Li-Al LDHs were modified by calcination and further modification after calcination with a silane coupling agent containing amine groups. Calcination caused the change of the catalysts' structure from a double-layer structure to porous particle and the specific surface area highly increased. After modification with a silane coupling agent, the average pore diameter increased. The two methods had a similar effect on catalytic activity improvement. However, modifying with a coupling agent can sharply decrease the catalysts' regeneration temperature. Furthermore, catalyst recycling and regeneration, along with the effects of temperature, time, agitation, and ratio between SBO and ethylene glycol on transesterification were studied.