Perillartine (Ⅱ) was prepared by condensation reaction using perillaldehyde (Ⅰ) as starting material. Then, twenty-one perillaldehyde-based oxime esters (Ⅲa ～ u) were synthesized in 70% ~ 90% yields by O-acylation reaction of perillartine with a series of acyl chlorides. All the target compounds were characterized by FTIR, 1HNMR, 13CNMR, and ESI-MS. The herbicidal and antifungal activities were also evaluated in this study. The results showed that, at 100 mg/L, the target compounds perillaldehyde-based methyl oxime ester (Ⅲa) and perillaldehyde-based ethyl oxime ester (Ⅲb) had inhibition rates of 97.0% and 91.0% against seedling-growth of barnyard grass (Echinochloa crusgalli L.), respectively, displaying comparable herbicidal activity with the commercial herbicide flumioxazin with the inhibition rate of 97.5%. Perillaldehyde-based p-chlorophenyl oxime ester (Ⅲm) and perillaldehyde-based ethyl oxime ester (Ⅲb) had inhibition rates of 88.4% and 79.6% against the root of rape (Brassica campestris), exhibiting better herbicidal activity than the commercial herbicide flumioxazin with the inhibition rate of 63.0%. Besides, at 50 mg/L, the target compounds Ⅲa ～ u showed certain antifungal activities against Physalospora piricola, Fusarium oxysporum f. sp. Cucumerinum, Cercospora arachidicola, Fusarium graminearum and Alternaria solani, in which perillaldehyde-based ethyl oxime ester (Ⅲb) presented the best antifungal activity with the inhibition rates of 85.0% and 79.2% against C. arachidicola and P. piricola, respectively.