Preparation of microfibre constructs of collagen by electrospinning has been problematic due to the instability of collagen in volatile solvents, such as 1,1,1,3,3,3-hexafluoro-2-propanol, so that electrospinning leads to a substantial amount of gelatin fibres. In the present study we have demonstrated the production of collagen-based microfibre constructs by use of a layer-by-layer coating process onto a preformed synthetic polymer microfibre base. Soluble native collagen, which has a basic isoelectric point, has been used with modified triple-helical collagens that have acidic isoelectric points. These modified collagens have been prepared as deamidated, succinylated, maleylated and citraconylated derivatives. Together, the acidic and basic collagens have successfully coated polyacrylonitrile and poly(DL-lactide-co-glycolide) fibres, as shown by spectroscopy and microscopy. These coatings allow good cell attachment and spreading on the fibres. The native, triple helical form of the collagen has been confirmed through use of a conformation dependent monoclonal antibody. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.