The first amphiphilic sugar and deoxyuridine conjugates with a 4-ethynyl-1,8-N-methylnaphthalimide linker, a 4-ethynyldeoxyuridine conjugate with a N-undecylferrocenyl headgroup, and a 1,8-naphthalimide with a 2,3,4,6-tetra-O-acetate-β-d-glucopyranoside headgroup have been synthesized. A novel acrylate monomeric precursor for sugar–ethynylnaphthalimide polymers is also reported. The ethynyl tether forms complexes with Co₂(CO)₈ and Co₂(CO)₆dppm. The single-crystal X-ray structures of 2′-propynyl-2,3,4,6-tetra-O-acetate-β-d-glucopyranoside 4 and 4-(2′-propynyl-2,3,4,6-tetra-O-acetate-β-d-glucopyranoside)-N-methyl-1,8-naphthalimide 6 are also reported. With the exception of the Co₂ complexes, the sugar and deoxyuridine conjugates are strongly fluorescent. ‘On–off’ fluorescent switching is achieved in the deoxyuridine conjugate with an undecylferrocenyl headgroup.