Air pollution effects on cardiovascular hospitalizations in small urban/suburban areas have been scantly investigated. Such effects were assessed among the participants in the analytical epidemiological survey carried out in Pisa and Cascina, Tuscany, Italy (2009–2011). Cardiovascular hospitalizations from 1585 subjects were followed up (2011–2015). Daily mean pollutant concentrations were estimated through random forests at 1 km (particulate matter: PM10, 2011–2015; PM2.5, 2013–2015) and 200 m (PM10, PM2.5, NO2, O3, 2013–2015) resolutions. Exposure effects were estimated using the case-crossover design and conditional logistic regression (odds ratio—OR—and 95% confidence interval—CI—for 10 μg/m3 increase; lag 0–6). During the period 2011–2015 (137 hospitalizations), a significant effect at lag 0 was observed for PM10 (OR = 1.137, CI: 1.023–1.264) at 1 km resolution. During the period 2013–2015 (69 hospitalizations), significant effects at lag 0 were observed for PM10 (OR = 1.268, CI: 1.085–1.483) and PM2.5 (OR = 1.273, CI: 1.053–1.540) at 1 km resolution, as well as for PM10 (OR = 1.365, CI: 1.103–1.690), PM2.5 (OR = 1.264, CI: 1.006–1.589) and NO2 (OR = 1.477, CI: 1.058–2.061) at 200 m resolution; significant effects were observed up to lag 2. Larger ORs were observed in males and in subjects reporting pre-existent cardiovascular/respiratory diseases. Combining analytical and routine epidemiological data with high-resolution pollutant estimates provides new insights on acute cardiovascular effects in the general population and in potentially susceptible subgroups living in small urban/suburban areas.