The development of new optimized photoinitiators for the two-photon induced photopolymerization (TPIP) is essential in order to obtain high resolutions in this solid freeform fabrication process. Herein, we present the syntheses and characterizations of a series of efficient photoinitiators, comprising of a cross conjugated D-π-A-π-D system. The different donor- and acceptor functionalities of the investigated photoinitiators as well as the synthesis of targeted derivatives containing double and triple bonds in the conjugated backbone allowed the evaluation of structure-activity relationships. The basic photophysical properties as well as the activity and ideal processing window under TPIP conditions were investigated for each initiator and compared with typical commercially available one-photon initiator and with two highly potential initiators well known from literature. These tests figured out that the new chromophores are highly potential even at concentrations down to 0.05 wt%.