The crystal structure, electronic structure, and transport properties of crystals with the nominal composition Nb0.25Bi2Se3 are investigated. X-ray diffraction reveals that the as-grown crystals display phase segregation and contain major contributions of BiSe and the superconducting misfit layer compound (BiSe)1.1NbSe2. The inhomogeneous character of the samples is also reflected in the electronic structure and transport properties of different single crystals. Angle-resolved photoemission spectroscopy (ARPES) reveals an electronic structure that resembles poor-quality Bi2Se3 with an ill-defined topological surface state. High-quality topological surface states are instead observed when using a highly focused beam size, i.e., nanoARPES. While the superconducting transition temperature is found to vary between 2.5 and 3.5 K, the majority of the bulk single crystals does not exhibit a zero-resistance state suggesting filamentary superconductivity in the materials. Susceptibility measurements of the system together with the temperature dependence of the coherence length extracted from the upper critical field are consistent with conventional BCS superconductivity of a type II superconductor.