PF radicals in both their ground (X(3) Sigma(-)) and metastable (a 1 Delta) electronic states have been produced by the gas phase reaction of F atoms with phosphine in a discharge flow reactor and detected by mass selective resonance enhanced multiphoton ionization (REMPI) spectroscopy in the wavelength range 410-225 nm. Analysis of the longer wavelength end of this spectrum (lambda>328 nm) has enabled identification and spectroscopic characterization of five hitherto unknown Rydberg states of this radical. These we label the h(1) Sigma(+) (T-0=57 324.9 cm(-1)), D (3) Delta (T-0=58 223.0 cm(-1)), E (3) Sigma(-)(T-0=58 690 cm(-1)), i 1 Delta (T-0=59 881.6 cm(-1)), and j (1) Sigma(-) (T-0=61 873.9 cm(-1)) states, respectively. [Origins, relative to the lowest rovibrational level of the ground (X (3) Sigma(-)) state are indicated by the numbers in brackets.] Quantum defect arguments suggest that all five states derive from the electronic configuration [(2) Pi]4p pi(1). Within the shorter wavelength region we identify two additional sets of poorly resolved resonances which we associate with a further two Rydberg states belonging to series converging to the ground state ionization limit, followed by two extensive progressions of bands. Possible assignments for these two progressions are considered.