This article presents the synthesis and characterization of a series of cross-conjugated D-pi-A-pi-D-based photoinitiators for the two-photon-induced photopolymerization process. Different donor and acceptor functionalities and derivatives containing double and triple bonds in the conjugated backbone allowed the evaluation of structure-activity relationship. Investigation of the basic photophysical properties showed high extinction coefficients at around 400 rim and none or vanishingly small emission quantum yields. The evaluated initiators showed at least similar activity, and in some cases broader processing windows than well-known highly active initiators from the literature and by far better results than commercially available initiators in terms of two-photon-induced microfabrication. These results are well in accordance with the TPA cross section values for the compounds measured by z-scan analysis. By using optimized parameters, structures with line widths of about 250 nm were obtained at photoinitiator concentrations as low as 0.05 wt %.