The single photonic quantum well (PQW) structures are successfully fabricated on p-type silicon wafer by electrochemical etching process, and are used for DNA detection firstly. The red shift of resonance peak is caused by the changing refractive index of PSi layer, which results from coupling of organic molecules into pores. When the porous silicon (PSi) based single PQW biosensors are immersed in complementary deoxyribonucleic acid (DNA) with different concentrations ranging from 0.625 μM to 10.000 μM, a good linear relationship is observed between the red shift of resonance peak and the complementary DNA concentration. Experimental results show that the detection sensitivity of PSi-based single PQW biosensors is 3.04 nm/μM with a detection limit of 32 nM for 16-base pair DNA oligonucleotides.