Compared to general document analysis tasks, form document structure understanding and retrieval are challenging. Form documents are typically made by two types of authors; A form designer, who develops the form structure and keys, and a form user, who fills out form values based on the provided keys. Hence, the form values may not be aligned with the form designer's intention (structure and keys) if a form user gets confused. In this paper, we introduce Form-NLU, the first novel dataset for form structure understanding and its key and value information extraction, interpreting the form designer's intent and the alignment of user-written value on it. It consists of 857 form images, 6k form keys and values, and 4k table keys and values. Our dataset also includes three form types: digital, printed, and handwritten, which cover diverse form appearances and layouts. We propose a robust positional and logical relation-based form key-value information extraction framework. Using this dataset, Form-NLU, we first examine strong object detection models for the form layout understanding, then evaluate the key information extraction task on the dataset, providing fine-grained results for different types of forms and keys. Furthermore, we examine it with the off-the-shelf pdf layout extraction tool and prove its feasibility in real-world cases.