Novel multiferroic materials have attracted increasing attention in recent years. Aurivillius bismuth-layer structured Bi4Ti3O12·nBiFeO3 (BTFO: n = 1–3, 5) compounds with potential multiferroic properties are such a compound. However, the data on these BTFOs are ambigious, inconsistent, and incomplete. Therefore BTFOs were grown into single crystals for a systematic evaluation. Their crystal structures and microstructures show that intergrowth of layer structure occurs easily in this class of material. Their ferroelectric measurements show strong anisotropy and dielectric peaks at high temperature, accompanied by an abnormal loss that corresponds to their polar phase transition. At room temperature, ferroelectric hysteresis loops were successfully measured; the loops show a strong dependence in their polarization and coercive field on different values of n and anisotropy. Magnetic measurement shows that all the single crystals display magnetic transitions at high temperatures and weak ferromagnetism at room temperature. Electron spin resonance (ESR) results show the coexistence of ferromagnetic and paramagnetic signal components in all the compounds. Scanning probe microscope measurements show magnetic domains switched together with electric domains by use of an electric field. Therefore we conclude that overall spin disorder with localized order is the character of this class of material, with observed magnetoelectric (ME) coupling. This work could also point the way to novel multiferroic materials in locally magnetic ordered systems.