The reaction of CH3NC with OH radicals was studied in smog chamber experiments employing PTR-ToF-MS and long-path FTIR detection. The rate coefficient was determined to be k(CH3NC+OH) = (7.9 +/- 0.6) x 10(-11) cm(3) molecule(-1) s(-1) at 298 +/- 3 K and 1013 +/- 10 hPa; methyl isocyanate was the sole observed product of the reaction. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemistry calculations showing the reaction to proceed primarily via electrophilic addition to the isocyanide carbon atom. On the basis of the quantum chemical data, the kinetics of the OH reaction was simulated using a master equation model revealing the rate coefficient to be nearly independent of pressure at tropospheric conditions and having a negative temperature dependence with k(OH) = 4.2 x 10(-11) cm(3) molecule(-1) s(-1) at 298 K. Additional quantum chemistry calculations on the CH3NC reactions with O-3 and NO3 show that these reactions are of little importance under atmospheric conditions. The atmospheric fate of methyl isocyanide is discussed.