As Large Language Models (LLMs) gain wider adoption, ensuring their reliable handling of Personally Identifiable Information (PII) across diverse regulatory contexts has become essential. This work introduces a scalable multilingual data curation framework designed for high-quality PII annotation across 13 underrepresented locales, covering approximately 336 locale-specific PII types. Our phased, human-in-the-loop annotation methodology combines linguistic expertise with rigorous quality assurance, leading to substantial improvements in recall and false positive rates from pilot, training, and production phases. By leveraging inter-annotator agreement metrics and root-cause analysis, the framework systematically uncovers and resolves annotation inconsistencies, resulting in high-fidelity datasets suitable for supervised LLM fine-tuning. Beyond reporting empirical gains, we highlight common annotator challenges in multilingual PII labeling and demonstrate how iterative, analytics-driven pipelines can enhance both annotation quality and downstream model reliability.