The specific relationship between the alkyl tail lengths of four azobenzene probes embedded in DOPC liquid disorder membrane and their (non) linear optical (NLO) properties have been considered in the current study. Using extensive molecular dynamics calculations, the push/pull effect of the alkyl tails on the position and orientation of the probes in the model membrane are discussed. The simulations indicate that with increasing tail lengths the cis isomers are pushed closer to the membrane surface, while the trans ones are rather pulled toward the membrane center. Throughout hybrid quantum mechanics/molecular mechanics calculations, the linear and nonlinear optical properties of these compounds have been investigated. The pushing effect of the tails for cis azobenzene is translated in strong responses in the (non) linear I optical spectroscopies, while the opposite is seen for the trans isomers. The cis isomer can be seen as the active state of the azobenzene compound for membrane recognition. The current work highlights the correlation between the tails of photosensitive membrane probes and their NLO properties, and focuses on unexpected behaviors of azobenzene derivatives in biological environments which can be exploited in distinguishing between soft and stiff cellular compartments that are of utmost importance for ion carrier transport.