Alternatives to commercial chemical herbicide are currently being searched and tested due to the numerous adverse effects of commercially available herbicides to the environment. Barnyardgrass (Echinochloa crusgalli) is an important weed species around the world, especially in paddy rice fields. This study focuses on the favorable effects of mixing pyroligneous acids with commercial liquid herbicides. Seedlings were transplanted and grown under greenhouse conditions. The effect of treatment time or leaf-stage on herbicide-pyroligneous acid efficacies was checked, coupled with isolation and quantification of biochemical compounds. Results revealed that herbicide treatment at early post emergence (2~3 leaf stage) of Echnochloa crus-galli leads to effective control. Both liquid herbicides affected fatty acid, protein, and amino acid syntheses as reflected on their contents. The influence of wood vinegar (WV) or rice vinegar (RV) on these compounds was not thoroughly verified due to lack of information on the pyroligneous products. We observed that mixing WV or RV with BCB (bentazone + cyhalof-butyl) gives more favorable results than BUC (butachlor + clomazone), mixed with WV or RV. The result would indicate the potential of mixing pyroligneous acid in reducing herbicide application rate.