The selection and use of chemicals and materials with less hazardous profiles reflects a paradigm shift from reliance on risk minimization through exposure controls to hazard avoidance. This article introduces risk assessment and alternatives assessment frameworks in order to clarify a misconception that alternatives assessment is a less effective tool to guide decision making, discusses factors promoting the use of each framework, and also identifies how and when application of each framework is most effective. As part of an assessor's decision process to select one framework over the other, it is critical to recognize that each framework is intended to perform different functions. Although the two frameworks share a number of similarities (such as identifying hazards and assessing exposure), an alternatives assessment provides a more realistic framework with which to select environmentally preferable chemicals because of its primary reliance on assessing hazards and secondary reliance on exposure assessment. Relevant to other life cycle impacts, the hazard of a chemical is inherent, and although it may be possible to minimize exposure (and subsequently reduce risk), it is challenging to assess such exposures through a chemical's life cycle. Through increased use of alternatives assessments at the initial stage of material or product design, there will be less reliance on post facto risk-based assessment techniques because the potential for harm is significantly reduced, if not avoided, negating the need for assessing risk in the first place.