Polydimethyl siloxane (PDMS) is the most widely used polymer in microfl uidic devices. Microfl uidic devices are used in all ranges of science. The microstructure of a microfl uidic device infl uences its effi ciency. One method for controlling microstructure is through wet etching. A particularly common etchant is tetrabutylammonium fl uoride (TBAF). This report shows that the etching rate of PDMS by a TBAF solution is controlled by the solvent in use. This report presents that solvent dictates interplay between the reactivity of the naked fl uoride with the Si O bonds in the polymer chain and the solubility of the polymer chains. Both high reactivity and accessibility are necessary for a high etching rate. This gives a simple method to control the etching rate of PDMS and by that the microstructure of the microfl uidic device.Dr. M. Kleiman, K. A. Ryu, Prof. A. P. Esser-Kahn Chemistry Department Natural Sciences II Irvine, CA 92697 , USA E-mail: aesserka@uci.edu One of the most common wet etchants for PDMS is tetrabutylammonium fl uoride (TBAF) [19][20][21] -owing to its rapid generation of "naked" fl uoride. Previously, researchers controlled the etching rate of PDMS by varying the fl ow rate and the concentration of TBAF. [ 22 ] They reported a maximum increase of 100% in etching rate by increasing fl ow rate as well as a structural change that depended on TBAF concentration. Here we show an increased etching rate of PDMS, up to two orders of magnitude, by changing the solvent. In these experiments, we use circular 3D channels and characterize the etching rate of the channels using TBAF dissolved in 16 common, organic solvents. Etching of PDMS by TBAF is currently thought to be mediated by the attack of the Si -O bonds of PDMS by the naked fl uoride. [23][24][25] The exact mechanism for the reaction between the naked fl uoride and the Si -O bonds remains unknown. From our current etching experiments, we demonstrate that the wide range of PDMS removal rates depends on two factors: (1) the reactivity of TBAF with Si -O bonds in the solvent, which in turn depends on the polarity of the solvent and (2) the degree of solvent swelling of PDMS.