Large Language Models (LLMs), such as ChatGPT, have achieved impressive milestones in natural language processing (NLP). Despite their impressive performance, the models are known to pose important risks. As these models are deployed in real-world applications, a systematic understanding of different risks posed by these models on tasks such as natural language inference (NLI), is much needed. In this paper, we define and formalize two distinct types of risk: decision risk and composite risk. We also propose a risk-centric evaluation framework, and four novel metrics, for assessing LLMs on these risks in both in-domain and out-of-domain settings. Finally, we propose a risk-adjusted calibration method called DwD for helping LLMs minimize these risks in an overall NLI architecture. Detailed experiments, using four NLI benchmarks, three baselines and two LLMs, including ChatGPT, show both the practical utility of the evaluation framework, and the efficacy of DwD in reducing decision and composite risk. For instance, when using DwD, an underlying LLM is able to address an extra 20.1% of low-risk inference tasks (but which the LLM erroneously deems high-risk without risk adjustment) and skip a further 19.8% of high-risk tasks, which would have been answered incorrectly.