Four analogues of cannabidiol (CBD) were synthesized from Friedel-Crafts alkylation with α-phellandrene as alkylation reagent, phloroglucinol or alkylphenol as the nucleophilic receptor under the catalysis of ferric chloride. Meanwhile, other eight cannabinol analogues were synthesized by O-alkylation with alkyl bromide using 8,9-dihydrocannabidiol (H2CBD) and 2,2,8,9-tetrahydrocannabinol (2,2,8,9-THC). The antioxidant activities of CBD and its analogues were characterized by DPPH, ABTS free radical scavenging ability and inhibition on lipid oxidation, and their antibacterial activities against four bacteria were studied. The relationship between the structure of the analogues and the properties was investigated. The reduction of phenolic hydroxyl groups on the benzene ring resulted in weakening of the antibacterial and antioxidant activity. The results showed that analog I, due to its polyphenolic structure, performed better antioxidant capacity than CBD did, and its EC50 values of DPPH and ABTS free radical scavenging were 23.8% and 25.1% of that of CBD, respectively; which is even slightly lower than that of VC. Analogues I presented good antibacterial activity against the assayed bacteria with the minimum antibacterial concentration (MIC) lower than 100 μg/mL; whereas other analogs exhibited no antibacterial activity against the above bacteria at the assayed concentrations. Overall, phenolic hydroxyl group maybe essential for antioxidant and antibacterial activity of CBD analogues.