With technological development, the rapid growing numbers of electronic devices generate severe electromagnetic interference (EMI) and radiation to human environment. In this study, the coupling effect of graphene oxide (GO) addition (up to 0.10 wt.% of cement) and waste cathode-ray tube (CRT) glass replacement for fine aggregates (30 and 60 wt.%) in cement-based composites on mitigating EMI was studied. The electric permittivity obtained using a decoupling method was applied for evaluating the EMI shielding capacity of cement-based composites, while direct current (DC) electrical resistance measurement is conducted using four-probe method. The DC electrical resistivity of specimens increases insignificantly with increasing in GO content, but remarkably with increasing CRT glass content from 30 to 60 wt.%. The 60 wt.% replacement of waste CRT glass with 0.1 wt.% GO addition increases the relative permittivity by about 50% and 200% when the frequency is in the ranges of 104-5 x 106 Hz and 101-103 Hz, respectively. It is concluded that a significant increase in the permittivity can be obtained owing to the synergetic interaction between waste CRT glass and GO. The improvement in the EMI shielding ability of cement-based composites not only enables the applications of these composites in mitigating electromagnetic pollution, but also promotes large-volume recycling of toxic waste CRT glass.