Porous semiconductors structured top-down by electrochemical means, and from bottom-up growth of arrays and arrangements of nanoscale structures, are shown to be amenable to a range of useful thermal, optical, electrical and electrochemical properties. This paper summarises recent investigations of the electrochemical, electrical, optical, thermal and structural properties of porous semiconductors such as Si, In2O3, SnO2 and ITO, and dispersions, arrays and arrangements of nanoscale structures of each of these materials. We summarize the property-inspired application of such structurally engineered arrangements and morphologies of these materials for antireflection coatings, broadband absorbers, transparent contacts to LEDs that improve transmission, electrical contact and external quantum efficiency. Additionally the possibility of thermoelectric performance through structure-mediated variation in thermal resistance and phonon scattering without a p-n junction is shown through phonon engineering in roughened nanowires. Lastly, we show that bulk crystals and nanowires of p- and n-type doped Si are promising for use as anodes in Li-ion batteries.