In unintentionally Nb-doped 4H-SiC grown by high-temperature chemical vapor deposition (HTCVD), an electron paramagnetic resonance (EPR) center with C-lh symmetry and an electron spin S=1/2 was observed. The spectrum shows a hyperfine structure consisting of ten equal-intensity hyperfine (hf) lines which is identified as due to the hf interaction between the electron spin and the nuclear spin of Nb-93. An additional hf structure due to the interaction with two equivalent Si neighbors was also observed. Ab initio supercell calculations of Nb in 4H-SiC suggest that Nb may form a complex with a C-vacancy (V-C) resulting in an asymmetric split-vacancy (ASV) defect, Nb-Si-V-C. Combining results from EPR and supercell calculations, we assign the observed Nb-related EPR center to the hexagonal-hexagonal configuration of the AVS defect in the neutral charge state, (Nb-Si-V-C)(0).