Pump/probe picosecond time-resolved resonance Raman spectra of nickel(II) octaethylporphyrin (NiOEP) in pyridine were observed in the time range -5 to +1000 ps. The spectra demonstrate generation of the vibrationally and electronically excited (d,d) state (B-1g) immediately after the excitation to the pi pi* state of the macrocycle, subsequent vibrational relaxation, and the formation of six-coordinate exciplex, B-1g(L)(2) (L = pyridine). Singular value decomposition analysis was applied to a series of picosecond time-resolved Raman spectra to investigate whether a five-coordinate complex was generated prior to the formation of the six-coordinate species. The results indicate insignificant population of the five-coordinate species preceding the formation of B-1g(L)(2) and suggest concerted coordination of two solvent molecules to axial positions of the (d,d) excited NiOEP. The formation process of the B-1g(L)(2) species is discussed.