Black carbon (BC) is the dominant component of the light absorbing aerosols in the atmosphere, changing earth's radiative balance and affecting the climate. The mixing state and size distribution of atmospheric BC are largely unknown and cause uncertainties in climate models. BC is also a major component of diesel PM emissions, recently classified by World Health Organization as Category I Carcinogen, and has been associated with various adverse health effects. This study presents a novel approach of direct and continuous measurement of BC mass size distribution by tandem operation of a differential mobility spectrometry and a refined Aethalometer. A condensation particle counter was deployed in parallel with the Aethalometer to determine particle number size distribution. A wide range of particle sizes (20–600 nm) was investigated to determine the BC modal characteristics in fresh diesel engine tailpipe emissions and in different urban environments including a typical urban ambient site and a busy roadside. The study provided a demonstration of a new analytic approach and showed the evolution of BC mass size distribution from fresh engine emissions to the aged aerosols in the roadside and ambient environments. The results potentially can be used to refine the input for climate modeling to determine the effect of particle-bound atmospheric BC on the global climate.