The prediction of pollutant emissions and fuel consumption under real operating conditions of any motor vehicle requires the use of complex mathematical models and experimental tools. In the present research, biharmonic maps (BM) were used to predict NOx (nitrogen oxides) emissions and relative fuel–air ratio (Fr) of a passenger city bus. For the collection of experimental data, an instrumented city bus was tested during real passenger transportation. The data were classified into four dynamic sequences: acceleration, idling, deceleration with fuel consumption, and deceleration without fuel consumption. Among them, the acceleration sequence was selected due to high NOx emissions and high fuel consumption. Experimental results were in good agreement with BM predictions. Significant parameters for predicting NOx concentration were vehicle velocity and relative fuel–air ratio (Fr). While for predicting Fr, significant parameters were the exhaust gas flow (EGF) rate, vehicle velocity, and NOx concentration, BM is a good technique for predicting NOx emissions and Fr of a city bus under transient operation.