Electrospray is a widely recognized physical process and has various applications, such as in electrospinning, space propulsion, and mass spectrometry (MS). Particularly, electrospray emitters are integral to the exceptional performance of electrospray ionization mass spectrometry (ESI-MS). This study introduced a novel method for fabricating electrospray emitters using two-photon direct laser writing, resulting in the printing of nanosprayer arrays directly onto capillary tips. Utilizing a novel acrylic polyhedral oligomeric silsesquioxane photoresist, a multinozzle sprayer with micrometer scale channels was designed and printed on a capillary that is compatible with both frontend liquid chromatography and typical MS inlets. The 3D-printed sprayers demonstrated exceptional resistance to organic corrosion and high temperatures. For the nanosprayer arrays, an increase in the total electrospray current was achieved by augmenting the number of electrosprays, while maintaining a constant liquid flow rate and voltage. Notably, the eight-nozzle sprayers exhibited a 2.7-fold enhancement in sensitivity as compared with single-nozzle sprayers. This approach offers a versatile and high-sensitivity nanoelectrospray solution for ESI-MS.