In this paper an innovative structure/property approach is used to evaluate several commercially available surfactants in tests relevant to both alkaline-surfactant-polymer (ASP) and surfactant-polymer (SP) floods, in order to gain an understanding of how hydrophobe structure is related to surfactant performance and crude oil composition. The surfactant structural elements considered here include relative branching level and carbon chain length. This has application to chemical EOR implementation in fields over a range of reservoir temperatures and salinity. Phase behavior (giving interfacial tension), and micro-emulsion viscosity tests were carried out for internal olefin sulfonates and mixtures with alcohol propoxy sulfates to identify those that perform well while minimizing or eliminating the use of costly co-solvents. Hydrophobe branching and carbon chain length, characterized by gas chromatography, were used to match surfactants to certain crude oil properties such as natural surfactants, including total acid number (TAN) and asphaltenes, and the ratio of saturates/aromatics. The paper also examines how crude oil sampling influences crude properties and surfactant performance. The approach used and associated data contribute to cost reduction of formulations through a) better matching of commercially produced surfactants to the reservoir and crude oil properties to improve oil recovery efficiency, and b) minimizing or eliminating the use of co-solvents to reduce formulation and logistics costs. In addition, the study demonstrates how binary blends from a few core surfactants can match formulations across regionally different crude oils thereby simplifying formulation selection, and reducing uncertainty and cost.