Analyses of microchannel and microgap cooling show that galinstan, a recently developed nontoxic liquid metal that melts at −19 °C, may be more effective than water for direct liquid cooling of electronics. The thermal conductivity of galinstan is nearly 28 times that of water. However, since the volumetric specific heat of galinstan is about half that of water and its viscosity is 2.5 times that of water, caloric, rather than convective, resistance is dominant. We analytically investigate the effect of using structured surfaces (SSs) to reduce the overall thermal resistance of galinstan-based microgap cooling in the laminar flow regime. Significantly, the high surface tension of galinstan, i.e., 7 times that of water, implies that it can be stable in the nonwetting Cassie state at the requisite pressure differences for driving flow through microgaps. The flow over the SS encounters a limited liquid–solid contact area and a low viscosity gas layer interposed between the channel walls and galinstan. Consequent reductions in friction factor result in decreased caloric resistance, but accompanying reductions in Nusselt number increase convective resistance. These are accounted for by expressions in the literature for apparent hydrodynamic and thermal slip. We develop a dimensionless expression to evaluate the tradeoff between the pressure stability of the liquid–solid–gas system and hydrodynamic slip. We also consider secondary effects including entrance effects and temperature dependence of thermophysical properties. Results show that the addition of SSs enhances heat transfer.