Lead-free organic-inorganic hybrid perovskites have recently attracted intense interest as environmentally friendly, low-cost, chemically stable light absorbers. Here, we reported a new one-dimensional (1D) zigzag chainlike light-absorbing hybrid material of (C6H13N)2BiI5, in which the corner-sharing octahedral bismuth halide chains are surrounded by organic cations of tetramethylpiperidinium. This unique zigzag 1D hybrid perovskite-derivative material shows a narrow direct band gap of 2.02 eV and long-lived photoluminescence, which is encouraging for optoelectronic applications. Importantly, it behaves as a typical semiconducting material and displays obvious photoresponse in the visible-light range. This work opens a potential pathway for the further application of 1D lead-free hybrids.