Laboratory and greenhouse studies were conducted on redvine and trumpetcreeper to characterize leaf surface and wax composition, determine responses of these weeds to glyphosate, characterize the nature of interactions between glyphosate and several selective postemergence herbicides (e.g., acifluorfen, bentazon, chlorimuron, imazaquin, and pyrithiobac) used in soybean and cotton, and determine the effects of various adjuvants on glyphosate activity on both species. Trumpetcreeper was consistently more susceptible to glyphosate than redvine. Glyphosate spray solution droplets had lower contact angle in trumpetcreeper than in redvine. Micro-roughness of the trumpetcreeper adaxial leaf surface was greater due to trichomes and glands compared to that of redvine, which had no trichomes or glands. Stomata or crystal wax deposition on the adaxial leaf surface were not observed in either species. The wax mass per unit area (22 to 37 µg cm−2) was similar regardless of the leaf age in both species. Epicuticular wax consisted of hydrocarbons, alcohols, acids, and triterpenes. Wax composition of young leaves of redvine was relatively hydrophilic (72% alcohols and acids, 24% hydrocarbons) compared to the hydrophobic components (23% alcohols and acids, 49% hydrocarbons) of old leaves. In contrast, wax of trumpetcreeper young leaves was relatively hydrophobic (9% alcohols and acids, 29% hydrocarbons), whereas old leaves had similar levels of hydrophilic and hydrophobic components (28% alcohols and acids, 31% hydrocarbons). Glyphosate mixed with selective postemergence herbicides were antagonistic when applied to redvine and trumpetcreeper, except acifluorfen. Various adjuvants did not increase glyphosate efficacy except ammonium sulfate, which increased glyphosate efficacy when applied alone to trumpetcreeper. These results showed that lower glyphosate efficacy was related to the more hydrophobic nature of redvine epicuticular waxes compared to that of trumpetcreeper.