Agricultural formulations (concentrates) containing hydrophobic active ingredients (AIs) are applied to crops by dilution in water to form spray solutions. Aqueous spray solutions are applied to crops. Typical liquid concentrates are formulated as (a) solvent-based emulsifiable concentrates, (b) water-based suspension concentrates, and (c) oil-based suspensions. Solid forms like water-dispersible granules for hydrophobic AIs and water-soluble granules for hydrophilic AIs also form the bulk of agricultural formulations. Efficacy of the active ingredients can depend upon the particle/droplet size distribution in the spray solution, and it can be advantageous to have sub-micron size AI distribution with additional protection against wash off. Global awareness and strong regulatory initiatives are the driving force for the design of green and environmentally friendly delivery matrices. The following approaches described in this paper are viable solutions to address green delivery targets. This paper will address typical examples of solvent-free water-based matrices capable of solubilizing hydrophobic active materials using water-soluble polymer–surfactant interactions. At very high dilutions, water-insoluble active ingredients remained stable at a sub-micron size distribution maintaining bio-activity. This polymer–surfactant interaction approach was extended to formulate water-insoluble polymers in water at sub-micron distribution. These polymer matrices were useful as additives in formulations, as well as tank mix additives providing several benefits, such as improved spreading, wetting, sticking, rain-fastness, and bio-efficacy.