This paper presents a thermodynamic analysis of a high-yield biochemical process for biofuel production from lignocelluosic biomass based on a previously proposed process. Unlike the standard biochemical process, which ferments sugar intermediates to ethanol, the process under consideration converts sugars to acetic acid which is esterified and hydrogenated to produce ethanol. This process has a significantly higher yield and produces no carbon dioxide. However, we find that the thermodynamic efficiency of the process is not increased in proportion to the yield gain. An additional survey of various biofuel production processes showed no direct correlation between yield and thermodynamic efficiency. This survey and the detailed thermodynamic analyses lead us to conclude that yield alone is an unreliable performance metric for biofuel technologies.