5-Nitro-2-(2＇-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2＇-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2＇-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 3-nitro-4-(2＇-vinyloxyethoxy)benzylidene (4b) were prepared by the condensation of 5-nitro-2-(2＇-vinyloxyethoxy)benzaldehyde (1) and 3-nitro-4-(2＇-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b and 4a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 5-6 having nitrooxybenzylidenemalononitrile and nitrooxycyanocinnamate, which is effective chromophore for second-order nonlinear optical applications. Polymers 5-6 were soluble in common organic solvents such as acetone and DMSO. T-g values of the resulting polymer were in the range of 70-81 degrees C. Electrooptic coefficient (r(33)) of the poled polymer films were in the range of 19-27 pm/V, which was improved by introducing of nitro group. Polymers 5-6 showed a thermal stability up to 300 degrees C in TGA thermograms, which is acceptable for NLO device applications.