This work enlighten on the modification of the electrical and optoelectronic properties at metal/silicon interface, where the silicon surface is nanostructured by single step mask-less CF4 plasma in reactive ion etching mode. The electrical transport across metal/nanotextured silicon/silicon structure has been correlated with morphological variations of surface topological features and chemistry. The results evidence that such nanostructures enhance the photovoltaic behavior and affect electrical and optoelectronic transport to a different extent, depending not only on surface texturing but also on surface chemistry. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4710989]