The rate coefficients of the elementary reactions of metastable electronically excited CF2(ã 3B1) with NO and H2 have been determined for the first time over an extended temperature range (287 K–600 K). CF2(3B1) radicals were generated by pulsed laser photolysis of C2F4 at 193 nm and real-time pseudo-first-order decays of the relative CF2(3B1) concentration were obtained by monitoring the CF2(3B1 → 1A1) emission at 570–700 nm. Over the experimental temperature range, the rate coefficient of CF2(ã 3B1) + NO exhibits a marked negative temperature dependence: kNO(T) = (9.7 ± 2.5) × 10−12 exp[+(545 ± 80)K/T] cm3 s−1 molecule−1. For the removal of CF2(ã 3B1) by H2, only an upper limit of kH2 ≤ 3 × 10−14 cm3 s−1 molecule−1 could be established over this temperature range.