Hydrogenated nanocrystalline silicon (nc-Si:H) is a promising absorber material for photovoltaic applications. Nanoscale electrical conductivity and overall electronic quality of this material are significantly affected by film microstructure, specifically the density and dimension of grains and grain-boundaries (GB). Local charge distribution at grains and grain/GB interfaces of nc-Si:H was studied by Electrostatic Force Microscopy (EFM) in constant force mode under illumination of white LED. Bias voltage from -3V to +3V was applied on the tip. Scanning Kelvin Force (KFM) images were taken before and after illumination to study the change in surface photovoltage (SP). EFM and KFM analysis were combined with film topography to draw a correlation between surface morphology and nanoscale charge distribution in this material. After illumination, small blister like structures were observed whose size and density increase with time. Raman spectroscopy confirmed these new structures as nanocrystalline silicon. This change was assumed due to relaxation of strained Si-Si bonds as an effect of photo response. Nanocrystalline grain interiors were at lower potential and amorphous grain boundaries were at higher potential for negative bias; it was opposite for positive bias. Change in polarity in bias voltage reversed the polarity of the potential in grains and GBs indicating the dominance of negative type of defects. Further study with current sensing AFM in dark and illumination with variable bias voltages will be able to identify the type and density of defects in grains and grain/GB interfaces.