A sequence of chemical vapor synthesis and thermal annealing in defined gas atmospheres was used to prepare phase-pure anatase TiO2 nanocrystal powders featuring clean surfaces and a narrow particle size distribution with a median particle diameter of 14.5 ± 0.5 nm. Random networks of these nanocrystals were immobilized from aqueous dispersions onto conducting substrates and are introduced as model systems for electronic conductivity studies. Thermal annealing of the immobilized films at 100 °C < T < 450 °C in air was performed to generate particle-particle contacts upon virtual preservation of the structural properties of the nanoparticle films. The distribution of electrochemically active electronic states as well as the dependence of the electronic conductivity on the Fermi level position in the semiconductor films was studied in aqueous electrolytes in situ using electrochemical methods. An exponential distribution of surface states is observed to remain unchanged upon sintering. However, capacitive peaks corresponding to deep electron traps in the nanoparticle films shift positive on the potential scale evidencing an increase of the trapping energy upon progressive thermal annealing. These peaks are attributed to trap states at particle-particle interfaces in the random nanocrystal network (i.e. at grain boundaries). In the potential region, where the capacitive peaks are detected, we observe an exponential conductivity variation by up to 5 orders of magnitude. The potential range featuring the exponential conductivity variation shifts positive by up to 0.15 V when increasing the sintering temperature from 100 °C to 450 °C. Importantly, all films approach a potential- and sintering-temperature-independent maximum conductivity of ~10-4 Ohm-1cm-1 at more negative potentials. Based on these results we introduce a qualitative model, which highlights the detrimental impact of electron traps located on particle-particle interfaces on the electronic conductivity in random semiconductor nanoparticle networks.