Valence bond configuration interaction (VBCI) is introduced in this paper. The method adds the dynamic correlation contribution by use of configuration interaction (CI) following a VBSCF calculation. The VBCI method allows various approaches with different structure selection procedures. VBCIS involves only single excitations, while VBCISD involves also doubles, and so on. VBCI(D, S) includes doubly excited structures for the active electron shell and singly excited structures for inactive pairs. Using perturbation theory, VBCIPT truncates less important excitations and estimates their contribution by an approximate perturbation theoretic formula. The methods were tested by calculating the bond energies of H
2
, LiH, HF, HCl, F
2
, and Cl
2
as well as the barriers of identity hydrogen abstraction reactions, X• + X′H → XH + X′• (X, X′ = CH
3
, SiH
3
, GeH
3
, SnH
3
, PbH
3
). Test calculations show the VBCISD results match those of the MO‐based CCSD method. The computational results of VBCI(D, S) and VBCIPT match those of VBCISD with much less computational effort. As a demonstration of the potential of the VBCI method, we calculated the barrier of the hydrogen exchange reaction. The value of 10.0 kcal mol
−1
of the VBCI barrier is in very good agreement with the most accurate barrier of MO–based methods.