Two chromophores with π-deficient quinoxaline (Q) core in the π-electron bridge together with dibutylaniline (DBA) donor moiety and tricyanofuranyl (TCF) or dicyanovinyl (DCV) acceptor moieties have been synthesized to investigate their macroscopic nonlinear optical (NLO) activity in guest-host materials. A distinctive feature of the 7-DBA-VQPhV-TCF chromophore is predominance of negative solvatochromism over the positive one, which is quite rarely met for the chromophores manifesting inverse solvatochromic behavior as well as the blue shift of the absorption maximum compared to the chromophore FTC with divinylthiophene π-bridge. Introduction of quinoxaline moiety in the conjugated bridge promotes the increase of thermal stability: Td of both compounds is higher than 225 °C. Density functional theory was used to calculate the chromophores first hyperpolarizability (β). Quadratic NLO response characterized by d33 coefficient was measured by SHG technique for thin guest-host polymer films. The influence of chromophore content on the NLO coefficient of 7-DBA-VQPhV-TCF/PMMA film has been investigated and the d33 value of this film reaches 108 pm/V at 25 wt% load. The poled film 7-DBA-VQPh-DCV/PMMA shows twice smaller d33 values (30 pm/V) at the same chromophore load (20 wt%).