Interaction between magma and carbonate plays a pivotal role in volcanic systems, yet its impact on magma transport properties remains inadequately explored. This study presents novel viscosity data on a leucite-bearing phonotephritic melt from the 472 CE Pollena eruption (Vesuvius, Italy), doped with varying amounts of CaO and CaO + MgO. The compositions match the chemistry of melt inclusions and interstitial glasses from skarns at Vesuvius, which have been interpreted as related to mixing of magma with different amounts of CaO and MgO derived from the host carbonates (limestone and dolostone). Viscosity measurements were conducted at both high (1150–1400 °C) and low temperatures (640–760 °C) by concentric cylinder viscometry, differential scanning calorimetry, and micropenetration methods. Through an integrated approach which combines Brillouin and Raman spectroscopy with the aforementioned techniques, we accurately predict the viscosity changes induced by magma‑carbonate interaction and identify the formation of nanoheterogeneities during low-temperature viscosity measurements. Notably, viscosity models from the literature fail to accurately reproduce our experimental data set at both high and low temperature. In the high-temperature regime, the addition of CaO induces a remarkable viscosity decrease, surpassing that produced by CaO + MgO addition. Furthermore, our findings reveal a significant viscosity/temperature crossover resulting from the addition of CaO and CaO + MgO to the melt phase. Undoped melt exhibits a higher viscosity compared to doped melts above 750 °C, with an inverse trend observed below this temperature threshold. Such rheological constraints may affect the mobility and mixing capability of melts exposed to different levels of carbonate assimilation.