Inorganic semiconductor ferroelectrics such as BiFeO3 have shown great potential in photovoltaic and other applications. Currently, semiconducting properties and the corresponding application in optoelectronic devices of hybrid organo-plumbate or stannate are a hot topic of academic research; more and more of such hybrids have been synthesized. Structurally, these hybrids are suitable for exploration of ferroelectricity. Therefore, the design of molecular ferroelectric semiconductors based on these hybrids provides a possibility to obtain new or high-performance semiconductor ferroelectrics. Here we investigated Pb-layered perovskites, and found the layer perovskite (benzylammonium)2PbCl4 is ferroelectric with semiconducting behaviours. It has a larger ferroelectric spontaneous polarization Ps=13 μC cm(-2) and a higher Curie temperature Tc=438 K with a band gap of 3.65 eV. This finding throws light on the new properties of the hybrid organo-plumbate or stannate compounds and provides a new way to develop new semiconductor ferroelectrics.