Human exposure to air pollution in many studies is represented by ambient concentrations from space-time kriging of observed values. Space-time kriging techniques based on a limited number of ambient monitors may fail to capture the concentration from local sources. Further, because people spend more time indoors, using ambient concentration to represent exposure may cause error. To quantify the associated exposure error, we computed a series of six different hourly-based exposure metrics at 16,095 Census blocks of three Counties in North Carolina for CO, NOx, PM2.5, and elemental carbon (EC) during 2012. These metrics include ambient background concentration from space-time ordinary kriging (STOK), ambient on-road concentration from the Research LINE source dispersion model (R-LINE), a hybrid concentration combining STOK and R-LINE, and their associated indoor concentrations from an indoor infiltration mass balance model. Using a hybrid-based indoor concentration as the standard, the comparison showed that outdoor STOK metrics yielded large error at both population (67% to 93%) and individual level (average bias between −10% to 95%). For pollutants with significant contribution from on-road emission (EC and NOx), the on-road based indoor metric performs the best at the population level (error less than 52%). At the individual level, however, the STOK-based indoor concentration performs the best (average bias below 30%). For PM2.5, due to the relatively low contribution from on-road emission (7%), STOK-based indoor metric performs the best at both population (error below 40%) and individual level (error below 25%). The results of the study will help future epidemiology studies to select appropriate exposure metric and reduce potential bias in exposure characterization.