Novel PMMASTOCNT matrices were created by opened-tip vertically aligned multiwalled carbon nanotubes (VAMWCNTs) with conformal coatings of strontium titanate (STO) and poly(methyl methacrylate) (PMMA). Emission threshold of 0.8 V/μm was demonstrated, about 5-fold lower than that of the as-grown VA- MWCNTs. This was obtained after considering the related band structures under the perspective of work functions and tunneling width as a function of the STO thickness. We showed that there is an optimum thickness of STO coatings to effectively reduce the work function of CNTs and yet minimize the tunneling width for electron emissions. Furthermore, simulation and modeling suggest that PMMASTOCNT matrices have suppressed screening effects and Coulombs’ repulsion forces between electrons in adjacent CNTs, leading to low emission threshold, high emission density, and prolonged emission stability. These findings are important for practical application of VA-MWCNTs in field emission devices, X-ray generation, and wave amplification.