This, among other reasons, is why grain ethanol was such a scam.
The worst mechanical processes, by contrast, usually get at least 10-15% efficiency. That's what photovoltaics can do, for example. Gasoline engines have a thermal efficiency of about 30%, diesel about 45%. Granted, you lose energy in the extraction/refining/transportation steps, but it's still an order of magnitude more efficient than photosynthesis.
The primary [photosynthetic] reactions have close to 100% quantum efficiency (i.e., one quantum of light leads to one electron transfer); and under most ideal conditions, the overall energy efficiency can reach 35%. Due to losses at all steps in biochemistry, one has been able to get only about 1 to 2% energy efficiency in most crop plants. Sugarcane is an exception as it can have almost 8% efficiency.