We report a photoelectron-imaging investigation of the chlorocyanomethyl radical (CHClCN) and the corresponding carbene (CClCN). The results are discussed in comparison with the corresponding dichloro- and dicyano-substituted species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of the pi-donor Cl and pi-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene. The vertical detachment energy (VDE) of CHClCN- is determined to be 2.39 +/- 0.04 eV, with the broad photoelectron band consistent with the significant geometry change predicted by theory for the detachment transition. The adiabatic electron affinity of CHCICN, EA = 1.86 +/- 0.08 eV, is estimated on the basis of the experimental VDE and the computed difference between the VDE and EA values. This result allows the calculation of the bond dissociation energy of chloroacetonitrile, DH298(H-CHCICN) = 87.0 +/- 2.7 kcal/mol. Photoelectron imaging of CClCN- reveals two main transitions, assigned to the singlet ((1)A') and triplet (()3A") states of the CC1CN carbene. The respective VDEs are 2.76 +/- 0.05 and 3.25 +/- 0.05 eV. The experimental results are in good agreement with the theoretically predicted singlet-triplet vertical energy gap at the anion geometry, but inconclusive with regard to the adiabatic singlet-triplet splitting in CClCN. Consistent with the experimental findings, ab initio calculations using the spin-flip approach in combination with the coupled-cluster theory, indicate that the (1)A' and (3)A" states are nearly degenerate, with the singlet state lying adiabatically only similar to 0.01 eV below the triplet.