The origin of the metallization of c-axis resistivity upon intercalation of iodine into Bi2Sr2CaCu2O8+delta has been studied by performing I L-I-edge angle-resolved X-ray absorption spectroscopic (XAS) analysis and the tight binding band calculation with the extended Huckel method. According to the polarized I LI-edge XAS analysis, it has become clear that there is a significant anisotropy in the I 5p hole distribution of the intercalated iodine layer. Compared to the E perpendicular toc spectrum, the E//c spectrum shows weaker intensity and higher energy for the white line feature corresponding to the 2s --> 5p(z) transition, indicative of a strong interaction between the BiO layer and the intercalated iodine molecule along the c-axis, Such an interpretation is further supported by the band calculation results showing a significant hybridization between the Bi 6s orbital and the I 5p(z) one. On the basis of these findings, it is concluded that the orbital overlap between Bi 6s and I 5p(z) opens a conduction channel along the c-axis, which leads to the metallization of out-of-plane resistivity upon iodine intercalation.