The progressive decrease in natural surfaces to create space for urban dwellers with the consequential changes caused to hydrological regime of an area is taking a toll on environmental resources. The Natural Resources Conservation Service (NRCS) Curve Number (CN) model (earlier known as Soil Conservation Service Curve Number, SCS-CN) is used in the present study for assessing temporal variations in surface runoff in upper catchment of Rispana River, Dehradun city, India. Also, the composite CN is calculated using vegetation-impervious surface-soil (V-I-S) fraction derived from spectral normalisation and linear spectral mixture analysis method while assigning initial CN for hydrologic soil-cover complex for five years during 1991 to 2018. The results indicated a steady rise in impervious surface fraction and consequent surface runoff (8.25%) from 1991 to 2018, while urban green space fraction has shown depleting trends in north and central part of the city. The level of imperviousness highlighted an over 60% of central part of the city as impervious, which gradually decreases outwards from the city. A positive correlation is observed between surface runoff and ISA (R2 varies between 0.62 and 0.89, p < 0.05), whereas inverse relationship is observed with vegetative cover in all sub-basins (R2 varies between 0.61 and 0.91, p < 0.05). The study demonstrates the potential of NRCS-CN model with inputs drawn from V-I-S fraction for simulating surface runoff and understanding the urban flood risk. The work would be useful for the urban dwellers, administrators and planners for better planning and sustainable development of urban areas.