Microscaling Floating-Point (MXFP) has emerged as a promising low-precision format for large language models (LLMs). Despite various post-training quantization (PTQ) algorithms being proposed, they mostly focus on integer quantization, while their applicability and behavior under MXFP formats remain largely unexplored. To address this gap, this work conducts a systematic investigation of PTQ under MXFP formats, encompassing over 7 PTQ algorithms, 15 evaluation benchmarks, and 3 LLM families. The key findings include: 1) MXFP8 consistently achieves near-lossless performance, while MXFP4 introduces substantial accuracy degradation and remains challenging; 2) PTQ effectiveness under MXFP depends strongly on format compatibility, with some algorithmic paradigms being consistently more effective than others; 3) PTQ performance exhibits highly consistent trends across model families and modalities, in particular, quantization sensitivity is dominated by the language model rather than the vision encoder in multimodal LLMs; 4) The scaling factor of quantization is a critical error source in MXFP4, and a simple pre-scale optimization strategy can significantly mitigate its impact. Together, these results provide practical guidance on adapting existing PTQ methods to MXFP quantization.