The potential energy surfaces of the two lowest-lying triplet electronic surfaces (3)A" and (3)A' for the O(P-3) + C2H2 reaction were theoretically reinvestigated, using various quantum chemical methods including CCSD(T), QCISD, CBS-QCI/APNO, CBS-QB3, G2M(CC, MP2), DFT-B3LYP and CASSCF. An efficient reaction pathway on the electronically excited (3)A' surface resulting in H(S-2) + HCCO(A(2)A') was newly identified and is predicted to play an important role at higher temperatures. The primary product distribution for the multistate multiwell reaction was then determined by RRKM statistical rate theory and weak-collision master equation analysis using the exact stochastic simulation method. Allowing for nonstatistical behavior of the internal rotation mode of the initial (3)A'' adducts, our computed primary-product distributions agree well with the available experimental results, i.e., ca. 80% H(S-2) + HCCO(X(2)A'' + A(2)A') and 20% CH2((XB1)-B-3) + CO-(X-1 Sigma(+)) independent of temperature and pressure over the wide 300-2000 K and 0-10 atm ranges. The thermal rate coefficient k(O + C2H2) at 200-2000 K was computed using multistate transition state theory: k(T) 6.14 x 10(-15)T (1.28) exp(-1244 K/T) cm(3) molecule(-1) s(-1); this expression, obtained after reducing the CBS-QCI/APNO ab initio entrance barriers by 0.5 kcal/mol, quasi-perfectly matches the experimental k( T) data over the entire 200-2000 K range, spanning 3 orders of magnitude.