To comply with future emission regulations for internal combustion engines, system-related cold start conditions in short-distance traffic constitute a particular challenge. Under these conditions, pollutant emissions are seriously increased due to internal engine effects and unfavorable operating conditions of the exhaust aftertreatment systems. As a secondary effect, the composition of the exhaust gases has a considerable influence on the deposition of aerosols via different deposition mechanisms and on fouling processes of exhaust gas-carrying components. Also, the performance of exhaust gas aftertreatment systems may be affected disadvantageously. In this study, the exhaust gas and deposit composition of a turbocharged three-cylinder gasoline engine are examined in situ upstream of the catalytic converter at ambient and engine starting temperatures of −22 °C to 23 °C using a Fourier-transform infrared spectrometer and a particle spectrometer. For the cold start investigation, a modern gasoline engine with series engine periphery is used. In particular, the investigation of the behavior of deposits in the exhaust system of gasoline engines during cold start under dynamic driving conditions represents an extraordinary challenge due to an average lower soot concentration in the exhaust gas compared to diesel engines and so far has not been examined in this form. A novel sampling method allows ex situ analysis of formed deposits during a single driving cycle. Both, particle number concentration and the deposition rate are higher in the testing procedure of real driving emissions (RDEs) than in the inner city part of the worldwide harmonized light vehicles test cycle (WLTC). In addition, reduced ambient temperatures increase the amount of deposits, which consist predominantly of soot and to a minor fraction of volatile compounds. Although the primary particle size distributions of the deposited soot particles do not change when boundary conditions change, the degree of graphitization within the particles increases with the increasing exhaust gas temperature.