Long document question answering (DocQA) aims to answer questions from long documents over 10k words. They usually contain content structures such as sections, sub-sections, and paragraph demarcations. However, the indexing methods of long documents remain under-explored, while existing systems generally employ fixed-length chunking. As they do not consider content structures, the resultant chunks can exclude vital information or include irrelevant content. Motivated by this, we propose the Multi-view Content-aware indexing (MC-indexing) for more effective long DocQA via (i) segment structured document into content chunks, and (ii) represent each content chunk in raw-text, keywords, and summary views. We highlight that MC-indexing requires neither training nor fine-tuning. Having plug-and-play capability, it can be seamlessly integrated with any retrievers to boost their performance. Besides, we propose a long DocQA dataset that includes not only question-answer pair, but also document structure and answer scope. When compared to state-of-art chunking schemes, MC-indexing has significantly increased the recall by 42.8%, 30.0%, 23.9%, and 16.3% via top k = 1.5, 3, 5, and 10 respectively. These improved scores are the average of 8 widely used retrievers (2 sparse and 6 dense) via extensive experiments.