A roll milled complex of Polyaniline (PANI) and Dodecylbenzenesulphonic acid (DBSA) is used with a cross-linked polymer Divinylbenzene (DVB), to prepare a conductive thermoset matrix with good environmental stability at room temperature. Upon heating, thermal doping of PANI-DBSA and curing of DVB occur simultaneously. Different amounts of DVB are used to prepare different samples and their properties are determined. Electrical & mechanical properties are measured. It has been shown that the electrical properties and mechanical properties of the composites are inversely proportional. It is demonstrated that the flexural modulus increases with an increase in DVB content, while the conductivity increases with an increase in PANI-DBSA content. The composite using roll-milled PANI-DBSA complex has shown better stability but lower electrical and mechanical properties as compared to the composite prepared using centrifugally mixed PANI-DBSA complex. An environmentally stable PANI-DBSA/DVB conductive thermosetting matrix is introduced in this work. FTIR spectra and UV-vis-NIR spectra are obtained to explain the effect of roll milling on PANI-DBSA and also the effect of DVB concentration on the composite. Thermal stability of the composites is determined using TGA analysis. The morphology of the samples is studied using SEM and the conductivity behavior is explained. (C) 2016 Elsevier Ltd. All rights reserved.