This study marks a significant advancement by harnessing Large Language Models (LLMs) for multi-intent spoken language understanding (SLU), proposing a unique methodology that capitalizes on the generative power of LLMs within an SLU context. Our innovative technique reconfigures entity slots specifically for LLM application in multi-intent SLU environments and introduces the concept of Sub-Intent Instruction (SII), enhancing the dissection and interpretation of intricate, multi-intent communication within varied domains. The resultant datasets, dubbed LM-MixATIS and LM-MixSNIPS, are crafted from pre-existing benchmarks. Our research illustrates that LLMs can match and potentially excel beyond the capabilities of current state-of-the-art multi-intent SLU models. It further explores LLM efficacy across various intent configurations and dataset proportions. Moreover, we introduce two pioneering metrics, Entity Slot Accuracy (ESA) and Combined Semantic Accuracy (CSA), to provide an in-depth analysis of LLM proficiency in this complex field.