In vitro fertilization-embryo transfer (IVF-ET) stands as one of the most prevalent treatments for infertility. During an IVF-ET cycle, the time interval between trigger shot and oocyte pickup (OPU) is a pivotal period for follicular maturation, which determines mature oocytes yields and impacts the success of subsequent procedures. However, accurately predicting this interval is severely hindered by the variability of clinicians'experience that often leads to suboptimal oocyte retrieval rate. To address this challenge, we propose ILETIA, the first machine learning-based method that could predict the optimal trigger-OPU interval for patients receiving progestin-primed ovarian stimulation (PPOS) protocol. Specifically, ILETIA leverages a Transformer to learn representations from clinical tabular data, and then employs gradient-boosted trees for interval prediction. For model training and evaluating, we compiled a dataset PPOS-DS of nearly ten thousand patients receiving PPOS protocol, the largest such dataset to our knowledge. Experimental results demonstrate that our method achieves strong performance (AUROC = 0.889), outperforming both clinicians and other widely used computational models. Moreover, ILETIA also supports premature ovulation risk prediction in a specific OPU time (AUROC = 0.838). Collectively, by enabling more precise and individualized decisions, ILETIA has the potential to improve clinical outcomes and lay the foundation for future IVF-ET research.