Background: Fine particulate matter (PM2.5) occurs within a mixture of other pollutant gases that interact and impact its composition and toxicity. To characterise the local toxicity of PM2.5, it is useful to have an index that accounts for the whole pollutant mix, including gaseous pollutants. We consider a recently proposed pollutant mixture complexity index (PMCI) to evaluate to which extent it relates to PM2.5 toxicity. Methods: The PMCI is constructed as an index spanning seven different pollutant, relative to the PM2.5 levels. We consider a standard two-stage analysis using data from 264 cities in the Northern Hemisphere. The first-stage estimates the city-specific relative risks between daily PM2.5 and all-cause mortality, which are then pooled into a second-stage meta-regression model with which we estimate the effect modification from the PMCI. Results: We estimate a relative excess risk of 1.0042 (95%CI: 1.0023 - 1.0061) for an IQR increase (from 1.09 to 1.95) of the PMCI. The PMCI predicts a substantial part of within country relative risk heterogeneity with much less between-country heterogeneity explained. The AIC and BIC of the main model are lower than those of alternative meta-regression models considering the oxidative capacity of PM2.5 or its composition. Conclusions: The PMCI represents an efficient and simple predictor of local PM2.5-related mortality, providing evidence that PM2.5 toxicity depends on the surrounding gesous pollutant mix. With the advent of remote sensing for pollutants, the PMCI can provide a useful index to track air quality.