Studies that analyse the impact on mortality of particulate matter (PM) produced by biomass combustion from wildfires mostly focus on a single city or on cities in different countries, with very few concentrating on one country as a whole. Accordingly, the aim of this paper was to analyse the impact that PM has on daily mortality in Spain on days with biomass combustion from wildfires. To analyse natural PM advections the Ministry of Agriculture and Fishing, Food & Environment divides Spain into 9 geographical regions. One province representative of each region for was selected analysis purposes, with provincial daily natural-cause mortality across the period 2004–2009 as the dependent variable, and daily mean PM concentrations in the provincial capital as the independent variable. We controlled for the effect of other chemical pollutants (NO2 and O3), maximum daily temperature on heat-wave days, day of the week, trends, seasonalities and the autoregressive nature of the series, using generalised linear models with the Poisson regression link to calculate relative risks (RRs) and the increase in RR (IRR) of PM-related mortality. The analysis was performed for days with and without biomass advections (DBA and DNBA respectively), with a breakdown by year, summer, and the remainder of the year (i.e., excluding summer). The results indicated that daily mean PM concentrations were higher on DBA than on DNBA, with statistically significant differences in most provinces. Furthermore, PM10 was associated with higher daily mortality on DBA in regions where wildfires were most frequent, but not in the remaining provinces. This translated as an IRR per 10 μg/m3 of PM of 7.93 (2.36–13.81) in the North-west, 3.76 (1.36–6.22) in the Centre and 4.46 (2.99–5.94) in the South-west, values which in all cases were statistically higher than those obtained on DNBA. The increase in PM caused by biomass advections from wildfires is linked to a significant IRR of mortality in Spain. Hence, the fact that wildfires are likely to become increasingly frequent in the context of climate change makes this type of analysis particularly necessary.