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We present measurements of the excitation spectra from the 2p53p [5/2]3,2 levels in neon using two-step laser excitation and ionization in conjunction with an optogalvanic detection in dc and rf discharge cells. The 2p53p [5/2]3,2 intermediate levels have been approached via the collisionally populated 2p53s [3/2]2 metastable level. The Rydberg series 2p5(²P3/2)nd [7/2]4 (12 ≤ n ≤ 44), 2p5(²P3/2)ns [3/2]2 (13 ≤ n ≤ 35) and the parity forbidden transitions 2p5(²P3/2)np [5/2]3 (13 ≤ n ≤ 19) have been observed from the 2p53p [5/2]3 level, whereas the 2p5(² P3/2)nd [7/2]3 (12 ≤ n ≤ 44), 2p5(²P3/2)ns [3/2]2 (13 ≤ n ≤ 35), and 2p5(²P1/2)nd' [5/2]3 (9 ≤ n ≤ 12) Rydberg series have been observed from the 2p53p[5/2]2 level in accordance with the ΔJ = ΔK = ± 1 selection rules. The photoionization cross sections from the 2p53p [5/2]3 intermediate level have been measured at eight ionizing laser wavelengths (399, 395, 390, 385,380, 370, 364, and 355 nm) and that from the 2p53p [5/2]2 level at 401.8 nm. These measurements are in excellent agreement with the experimental values reported in the literature, while the experimental data lie much below the theoretically calculated photoionization cross sections curve. [ABSTRACT FROM AUTHOR]