Reducing ambient concentrations of nitrogen dioxide (NO2) remains a key challenge across many European urban areas, particularly close to roads. This challenge mostly relates to the lack of reduction in emissions of oxides of nitrogen (NOx) from diesel road vehicles relative to the reductions expected through increasingly stringent vehicle emissions legislation. However, a key component of near-road concentrations of NO2 derives from directly emitted (primary) NO2 from diesel vehicles. It is well-established that the proportion of NO2 (i.e. the NO2/NOx ratio) in vehicle exhaust has increased over the past decade as a result of vehicle after-treatment technologies that oxidise carbon monoxide and hydrocarbons and generate NO2 to aid the emissions control of diesel particulate. In this work we bring together an analysis of ambient NOx and NO2 measurements with comprehensive vehicle emission remote sensing data obtained in London to better understand recent trends in the NO2/NOx ratio from road vehicles. We show that there is evidence that NO2 concentrations have decreased since around 2010 despite less evidence of a reduction in total NOx. The decrease is shown to be driven by relatively large reductions in the amount of NO2 directly emitted by vehicles; from around 25 vol% in 2010 to 15 vol% in 2014 in inner London, for example. The analysis of NOx and NO2 vehicle emission remote sensing data shows that these reductions have been mostly driven by reduced NO2/NOx emission ratios from heavy duty vehicles and buses rather than light duty vehicles. However, there is also evidence from the analysis of Euro 4 and 5 diesel passenger cars that as vehicles age the NO2/NOx ratio decreases. For example the NO2/NOx ratio decreased from 29.5 ± 2.0% in Euro 5 diesel cars up to one year old to 22.7 ± 2.5% for four-year old vehicles. At some roadside locations the reductions in primary NO2 have had a large effect on reducing both the annual mean and number of hourly exceedances of the European Limit Values of NO2.