Dendritic calcite forms in an active cold-water tufa system in association with extracellular polymeric substances (EPS) that discontinuously coat bryophytes and cyanobacteria. Dendrites consist of 100–200 nm thick calcite fibres that form 3D lattice-like domains. In each dendrite domain, fibres have three structurally equal orientations, which correspond in disposition to radii from the centre of a calcite unit cell to the convex triple face junctions on its surface. Fibres do not form in the orientation of the c-axis. The external form of each dendrite has the shape of half of a shortened octahedron, with an upper triangular surface parallel to the substrate. Dendrite nucleation takes place on or in microbial EPS, whether microbial cells are present or not, and is probably effected by attraction of Ca2+ cations to negatively charged EPS, together with CO2-degassing and concomitant pH increase of supersaturated spring water in stream splash zones. Ensuing dendrite growth is abiogenic and controlled by diffusion. Dendrite c-axes are perpendicular to the substrate, probably because the negative charge of EPS forces the orientation of Ca2+ and CO planes within the developing dendrite crystal to be parallel to the EPS film surface. Dendrites are eventually filled and overgrown by solid, syntaxial calcite, which gradually and completely obliterates the dendrites as more familiar calcite crystal forms develop. No trace of the dendritic nucleus remains in the rock record. Calcite crystal nucleation may take place by this mechanism in many marine and meteoric settings, given that microbial EPS is now assumed to be virtually ubiquitous in these environments. This phenomenon could contribute to the development of familiar fabrics such as marine micrite cement and fibrous calcite cement, radial ooids, peloids, ‘abiogenic’ stromatolites, sea floor precipitates, microbialites, tufa, travertine, speleothems, and some meteoric cements. It may also contribute to the substrate-normal orientation of c-axes of common cement fabrics.