Vaporizable hydrocarbon-in-fluorocarbon endoskeletal droplets are a unique category of phase-change emulsions with interesting physical and thermodynamic features. Here, we show microfluidic fabrication of various morphologies, such as solid-in-liquid, liquid-in-solid, and Janus-type, of complex solid n-C20H42 or n-C21H44 and liquid n-C5F12 droplets. Furthermore, we investigated the vaporization behavior of these endoskeletal droplets, focusing on the effects of heat treatment and core size. Comparison of vaporization and differential scanning calorimetry results indicated that vaporization occurs prior to melting of the bulk hydrocarbon phase for C20H42/C5F10 droplets and near the rotator phase for C21H44/C5F10 droplets. We found that heat treatment of the droplets increased the fraction of droplets that vaporized and also increased the vaporization temperature of the droplets, although the effect was temporary. Furthermore, we found that changing the relative size of the solid hydrocarbon core compared to the surrounding liquid shell increased the vaporization temperature and the vaporizing fraction. Taken together, these data support the hypothesis that surface melting behavior exhibited by the linear alkane may trigger the fluorocarbon vaporization event. These results may aid in the understanding of the interfacial thermodynamics and transport and the engineering of novel vaporizable endoskeletal droplets for biomedical imaging and other applications.