Here we discuss the thermotropic and electrochemical properties and polymerisation of a series of N-substituted pyrrole monomers bearing mesogenic 4-substituted azobenzene attached as a pendant group via alkyl spacers. We discuss the effect upon these molecular properties of chain length and substitution of the azobenzene moiety with methoxy, cyano and nitro terminal groups. Additionally we present here the first crystal structure determination and analysis of two N-alkylpyrroles bearing mesogenic groups.