The material world is recently and very rapidly changing; altering the relationships between materials – the substance of everyday life – and designers – the professionals who are responsible for transforming materials into daily life objects. This vibrant context prompts us to explore and attempt to conceptualise these fluid relationships and review conceptual tools that will help to open up the scope of materials based research in design. To address the multiple and multi-faceted relationships designers are situated in, we borrow concepts from social sciences that explore materiality within its multiple environments. We draw on conceptualisations of materials as active and as having capacities to bring about change and proliferate relations, and responding to new developments of biotic materials. By considering historic materials, particularly milk-based plastics, we propose a new category of autonomous materials. We discuss the emerging designer-material relationships with the hope of directing future enquiry into materials and discuss the implications of a new class of materials – the ‘autonomoids’ – for design research.