Diode infrared laser absorption spectroscopy was used to measure the rate constant (k(1)) of the CN + CS2 reaction for the first time. k(1) was determined to be substantially pressure dependent with a value k(1) = (7.1 +/- 0.2 to 41.9 +/- 2.9) x 10(-12) cm(3) molecule(-1) s(-1) over 2-40 Torr at 298 K. The potential energy surface (PES) of the reaction was calculated using an ab initio method at B3LYP/6-311++G(d, p)//CCSD(T)/6-311++G(d, p) level of theory. Both experimental and computational results suggest that collision stabilization of the adduct NCSCS may dominate the reaction. The rate constant of the CN + SO2 reaction was measured to be very slow with an upper limit of k(2) <= 3.1 x 10(-14) cm(3) molecule(-1) s(-1), in disagreement with an earlier reported measurement. The PES of this reaction reveals an entrance barrier against formation of the low energy adduct NCOSO, in agreement with the experimental result.