We consider optimal regimes for algorithm-assisted human decision-making. Such regimes are decision functions of measured pre-treatment variables and, by leveraging natural treatment values, enjoy a "superoptimality" property whereby they are guaranteed to outperform conventional optimal regimes. When there is unmeasured confounding, the benefit of using superoptimal regimes can be considerable. When there is no unmeasured confounding, superoptimal regimes are identical to conventional optimal regimes. Furthermore, identification of the expected outcome under superoptimal regimes in non-experimental studies requires the same assumptions as identification of value functions under conventional optimal regimes when the treatment is binary. To illustrate the utility of superoptimal regimes, we derive new identification and estimation results in a common instrumental variable setting. We use these derivations to analyze examples from the optimal regimes literature, including a case study of the effect of prompt intensive care treatment on survival.