Methods for analyzing for silicon and silicone in biological matrixes were developed. A silicone-specific technique involved microwave digestion of samples in acid solution to rapidly break down the biological matrix while hydrolyzing silicones to monomeric species. The resulting monomeric silanol species were then capped with trimethylsilyl groups, extracted into hexamethyldisiloxane, and analyzed by gas chromatography. In serum, positive identification of silicone species with detection limits below 0.5 microgram of Si/mL are possible with this technique. The technique is compared with a silicone-specific technique, 29Si NMR, and a non-silicone-specific technique, ICP-AES. 29Si NMR was far less sensitive, with a detection limit of only 64 micrograms of Si/mL in serum when analyzing for one compound with a single sharp resonance. Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) has potentially lower detection limits, but the technique is not silicone-specific and suffers from species-dependent responses.