Polyperinaphthalenic organic semiconductor (PPNOS) nano-particles are prepared by excimer laser ablation (ELA) of a 3, 4, 9, lO-perylenetetracarboxylic dianhydride (PTCDA) target using XeC1 excimer laser beams. Heterojunctions of the films consisting of nano-particles of PPNOS with Si wafers are fabricated. Well rectifier property is obtained for the junction ofthe PPN with a n-Si substrate. Current versus voltage curves of the heterojunction in the dark and under illumination show that the junction is promisimg as a photovoltaic cell. Furthermore, the films are applied to anode electrodes for ultra thin rechargeable Li ion batteries. In-situ Raman spectroscopy of the films under lithium ion doping and undoping is performed to elucidate the storage mechanism of lithium ion at cis-polyacetylene-type edge (phenanthrene-edge) of PPN structure.