In this study, we employ an evolutionary algorithm in conjunction with first-principles density functional theory (DFT) calculations to comprehensively investigate the structural transitions, electronic properties, and chemical bonding behaviors of XI3 compounds, where X denotes phosphorus (P) and arsenic (As), across a range of elevated pressures. Our computational analyses reveal a distinctive phenomenon occurring under compression, wherein the initially trigonal structures of PI3 (P 63) and AsI3 (R-3) undergo an intriguing transformation, leading to the emergence of six-coordinated monoclinic phases (C2/m) at 6 GPa and 2 GPa for PI3 and AsI3, respectively. These high-pressure phases exhibit their stability up to 10 GPa for PI3 and 12 GPa for AsI3. Notably, the resulting structures at elevated pressures bear striking resemblance to the widely recognized six-coordinated octahedral BiI3 crystal configuration observed at ambient conditions. While the phenomenon of heightened coordination is conventionally associated with heavier pnictide iodides such as SbI3 and BiI3 under ambient conditions due to heightened ionic character and relativistic effects in bismuth (Bi) and antimony (Sb), our findings accentuate that analogous structural transformations can also be induced in lighter elements like phosphorus (P) and arsenic (As) under the influence of pressure.