In order to find a solid base catalyst that can be used for the continuous production of oligoglycerol, Na+, K+, Ca2+, Sr2+, and Ba2+ were doped into ZrO2 by co-precipitation method to obtain Na/ZrO2, K/ZrO2, Ca/ZrO2, Sr/ZrO2, Ba/ZrO2, respectively, and the prepared catalyst was used to synthesize oligoglycerol. XRD, Raman, CO2-TPD and other methods were used to study the effects of doping different metal ions on the structure and surface alkalinity of the catalyst. GC, ICP and other methods were used to study the activity and stability of catalysts. The results showed that Na/ZrO2, K/ZrO2 were monoclinic phases, Ba/ZrO2 were tetragonal phases, Ca/ZrO2 and Sr/ZrO2 were cubic phases, and each catalyst showed different basic sites. Among the five catalysts, Ca/ZrO2 showed the best stability, Ca2+ leaching was 0.003%, and after halving the catalyst dosage and cycling for 4 times, the glycerol conversion rate remained above 22% and the catalyst recovery rate was above 95%. Under the conditions of Ca/ZrO2 dosage of 1 g, glycerol dosage of 100 g, reaction temperature of 270 °C, reaction temperature of 24 h, the yield of oligoglycerol was 73.05%, and the selectivity was 100%.