A series of mono- and bistriazine derivatives has been selectively prepared in high yields using sustainable procedures. Donor substituents have been introduced into the triazine ring, including pyrazolyl-substituted anilines and ortho-, meta- and para-phenylenediamine as pi-conjugated spacers. This method was used to build sigma-pi-sigma-A-sigma-D systems for monotriazines and D-sigma-A-sigma-pi-sigma-A-sigma-D systems for bistriazines. A study of the optoelectronic properties has been performed by UV-vis and fluorescence spectroscopy and by cyclic voltammetry. The monotriazines do not show any emission but the bistriazines are blue emitters and show an interesting solvatochromic effect with a large Stokes shift of more than 10000 cm-1 in some cases and quantum yields up to 23%. The optoelectronic properties depend on the conjugation and the position and the donor character of the substituents and the spacers. Cyclic voltammetry has been used to determine the energy levels (HOMO and LUMO) in the bistriazines. An increase in the energy of the HOMO and a decrease in the energy of the LUMO was observed on extending the conjugation. The title compounds showed interesting properties for use in optoelectronic devices, especially as blue emitters.