High-quality instruction data is critical for LLM alignment, yet existing open-source datasets often lack efficiency, requiring hundreds of thousands of examples to approach proprietary performance. In this work, we find that beyond the widely recognized importance of prompt-response quality, prompt difficulty itself plays a critical role in driving alignment gains. Motivated by this observation, we introduce PiKa, a data-efficient family of expert-level alignment datasets that concentrates supervision on high-difficulty instructions. The PiKa-SFT dataset contains only 30k examples, an order of magnitude fewer than state-of-the-art open datasets like Magpie-Pro. Despite its small size, fine-tuning Llama-3-8B-Base on PiKa-SFT even outperforms the official Llama-3-8B-Instruct model trained on over 10M proprietary examples on widely used benchmarks such as AlpacaEval 2.0 and Arena-Hard. We also validate the generalizability of PiKa across the Qwen2.5 series (0.5B-7B), consistently surpassing their official instruction-tuned counterparts. Additionally, we provide 30k high-quality preference optimization examples to further enhance alignment. Our results demonstrate that promising alignment is achievable with significantly reduced data, democratizing access for resource-constrained research. Our code and data will be available at https://github.com/SJY8460/PiKa.