Cenospheres are low-density and hollow microspheres derived from coal-fired power plant fly ash waste. This study aims to prepare ultra-light-weight (<1000 kg/m³ wet density) concrete using fly ash cenospheres (FAC). To begin with, FAC's shell thickness and the water absorption and desorption were characterized. A mixing procedure was designed to avoid the segregation between the FAC and cement slurry. FAC can affect the rheological properties of fresh mixture over time through absorption and desorption of free water. The presented ultra-light-weight concrete has several advantages compared to the ones prepared using foaming methods. First, shrinkage is significantly reduced due to FAC's internal restraint and curing effects. Secondly, it has good mechanical performance, especially in bending and is more environmentally friendly due to use of less cement. X-ray computed tomography illustrates that FAC ultra-light-weight concrete has smaller pores of more uniform size compared with those prepared using foaming methods. X-Ray diffraction, thermal gravimetry-derivative thermal gravimetry, fourier-transform infrared spectroscopy and scanning electron microscopy are employed for the hydration products and microstructure characterization. Outcomes prove that FAC can combine well with the cement matrix, and react with calcium hydroxide to produce C-A-S-H through pozzolanic reaction.