Bioherbicides can be defined as plant pathogens, phytotoxins derived from pathogens or other microorganisms, augmentatively applied to control weeds. Although many pathogens with bioherbicidal potential have been discovered, most lack sufficient aggressiveness to overcome weed defenses to achieve adequate control. Plants use various physical and biochemical mechanisms to defend against pathogen infectivity, including callose deposition, hydroxyproline-rich glycoprotein accumulation, pathogenesis-related proteins (PR-proteins), phytoalexin production, lignin and phenolic formation, and free radical generation. Some herbicides, plant growth regulators, specific enzyme inhibitors, and other chemicals can alter these defenses. Various pathogens also produce chemical suppressors of plant defenses. Secondary plant metabolism is a major biochemical pathway related to several defense processes. Increased activity of a key enzyme of this pathway, phenylalanine ammonia-lyase (PAL), is often a response to pathogen attack, as demonstrated in two weeds and their associated bioherbicidal pathogens: Alternaria cassiae on sicklepod and A. crassa on jimsonweed. Weakening of physical and biochemical defenses, and lowering of resistance to pathogen attack, may result from reduced production of phenolics, lignin, and phytoalexins caused by herbicides and other chemicals that affect cuticular component biosynthesis and/or key aspects of secondary plant metabolism. Potent PAL inhibitors [aminooxyacetic acid, α-aminooxy-β-phenylpropionic acid, and (l-amino-2-phenylethyl)phosphonic acid] have some regulatory action on secondary plant metabolism and pathogenicity. Various herbicides and other chemicals dramatically affect extractable PAL activity levels and/or substantially alter PAL product production. Some non-pathogenic organisms can alter herbicide efficacy, and some herbicides influence disease development in plants. Research has shown some synergistic interactions of microbes and chemicals with relevance to weed control. Further research on pathogen interactions with agrochemicals (or other chemicals/regulators) could result in increased efficacy of pathogen-herbicide combinations, reduction of herbicide and pathogen levels required for weed control, and expanded pathogen host range.