Organic-inorganic hybrid perovskites (OIHPs) of lead halides have played a significant role in the field of light-emitting devices and display systems. However, the potential toxicity of lead is considered as one of the main problems for further applications, and it is highly desirable to design the new lead-free OIHPs with outstanding white light emission. Herein, we present a new lead-free single-component hybrid as the potential white light-emitting semiconducting material, [4-methylpiperidinium]2SbCl5 (4-MPSC), which adopts the one-dimensional inorganic chains of corner-sharing SbCl6 octahedra. It is worth noting that 4-MPSC shows the Commission internationale de l'éclairage (CIE) chromaticity coordinates of (0.33, 0.32), which is highly close to the pure white light emission value of (0.33, 0.33). Meanwhile, the white-light emission of 4-MPSC shows an ultra-high color rendering index (CRI) value of 96.29. It is believed that such an ultra-high CRI value will fulfil the requirement for color-critical high-level potential applications. Moreover, 4-MPSC also exhibits semiconducting properties, as verified by the positive temperature-dependent conductivity along with an optical bandgap of 2.93 eV. This work will provide a pathway for further design of new white-light-emitting materials in the lead-free OIHP system.