The 2-benzazole-1,10-phenanthrolines and their chromium(III) complexes were synthesized and characterized by elemental and spectroscopic analyses as well as by single-crystal X-ray crystallography. X-Ray crystallographic analyses of C6 and C8 reveal an octahedral geometry around both chromium centers. The electronic spectra of the chromium complexes exhibit d-d transitions typically of a pseudo-octahedral coordinated d(3) ion, falling into the region nu(1)(4)A(2g)-->(4)T(2g) 600-700 nm,nu(2)(4)A(2g)-->(4)T(1g)(F) 430-470 nm, and the 10Dq values between 15674 and 16529 cm(-1). The variation of the heteroatoms (X = N, O, S) in benzazole group shows regular influence on the 10Dq values as 10Dq (O) > 10Dq (N) > 10Dq (S), which reflects the sigma-donor/pi-acceptor properties of these benzazole ligands. Upon activation with modified methylaluminoxane (MMAO), these complexes exhibited high activities for ethylene oligomerization (up to 7.36 x 10(6) g mol(-1) (Cr) h(-1)) and ethylene polymerization (up to 1.28 x 10(6) g mol(-1) (Cr) h(-1)). The effects of non-coordinated N, O or S heteroatoms in the ligands have been examined, and interestingly catalytic activities also strictly adhered to the trend O > N > S under various ethylene pressures. Reaction conditions significantly influenced the catalytic properties of the complexes.