A new class of silicon-based chemical and biological sensors that offer an electrical response to a variety of substances is described. The devices utilize silicon flow-through sensing membranes with deep trench structures formed to depths up to 100μm, fabricated by electrochemical etching which transforms the silicon into macro-porous silicon (MPS). The sensors have demonstrated the ability to detect the presence of certain chemical and biological materials. Although the principle of operation of the devices is fairly complex, the transduction mechanisms can be compared to chemiresistors and chemically sensitive field-effect transistors (chemFETs). The electrical responses that have shown the most sensitivity are AC conductance and capacitance. Previous work has demonstrated that upon exposure to organic solvents (i.e. ethanol, acetone, benzene) the devices exhibit a characteristic impedance signature. The devices have also shown the ability to detect the hybridization of complementary DNA. The incorporation of other materials that have demonstrated sensitivity to low ambient levels of contaminants is also under investigation. The sensors have been designed and fabricated in linear array configurations; a microfluidic transport chip/package co-design is currently in progress.