The linear and nonlinear optical properties of well‐ordered Y‐type Langmuir–Blodgett (LB) multilayers of 2‐docosylamino‐5‐nitropyridine (DCANP) have been investigated. The nonlinear optical susceptibilities have been determined for the wavelengths &lgr;=1064 nm [d33=(7.8±1) pm/V,d31=(2.0±0.5) pm/V] and &lgr;=1318 nm [d33=(5.6±1) pm/V]. In first waveguiding experiments carried out TE0and TM0modes propagating over more than 20 mm could be excited. Coupling experiments allowed the determination of the dispersion of the refractive indexn3(n632.8 nm3=1.598). Guided wave attenuation coefficients as low as 12 dB/cm (at the wavelength &lgr;=632.8 nm) are reported.