Substitutional doping has traditionally been used to modulate the existing properties of semiconductors and introduce new exciting properties, especially in two-dimensional materials. In this work, we have investigated the impact of substitutional doping (using group III, IV, V, and VI dopants) on the structural, electronic, spin, and optical properties of GeSe monolayer by using first-principles calculations based on density functional theory. Our calculated binding energies, formation energies and phonon dispersion curves of the doped systems support their stability and hence the feasibility of physical realization. Our results further suggest that switching between metallic and semiconducting states of GeSe monolayer can be controlled by dopant atoms with a different number of valence electrons. The band gap of the semiconducting structures can be tuned within a range of 0.2864 eV to 1.17 eV by substituting with different dopants. In addition, most of the doped structures maintain the low effective mass, 0.20
m
0
to 0.59
m
0
for electron and 0.21
m
0
to 0.52
m
0
for hole, which ensures the enhanced transport properties of GeSe based electronic devices. Moreover, when Ge is substituted with group V dopants, a magnetic moment is introduced in an otherwise non-magnetic GeSe monolayer. The optical absorption coefficient of the doped structures can be significantly improved (>2×) in the visible and infrared regions. These intriguing results would encourage the applications of doped GeSe monolayer in next-generation electronic, optoelectronic and spintronic devices.