A molecular electrostatic potential (MESP) topographical study has been conducted for a variety of conjugated hydrocarbons at B3LYP/6-311+G(d,p) level of theory to understand their pi-conjugation features and aromaticity. The value of MESP minimum (V-m) is related to the localized and delocalized distribution of pi-electron density. The V-m values are located interior to the rings in polycyclic benzenoid hydrocarbons (PBHs), whereas they lie outside the boundary of the rings in antiaromatic and in fused systems consisting of aromatic and antiaromatic moieties. The V-m points lie on top and bottom of the pi-regions in linear polyenes and annulenes, while a degenerate distribution of CPs around the midpoint region of triple bonds is observed in alkynes. The eigenvalues lambda(1), lambda(2), and lambda(3), of the Hessian matrix at V-m (MESP minima) are used to define the aromatic character of the cyclic structures. The eigenvalues follow the trend lambda(1) >> lambda(2) > lambda(3) congruent to 0 in PBHs, lambda(1) > lambda(2) > lambda(3) congruent to 0 in linear polyenes, and lambda(1) > lambda(2) > lambda(3) not equal 0 in antiaromatic systems. The difference in the aromatic character of PBHs from that of benzene is related to the deviations Delta lambda(1), Delta lambda(2), and Delta lambda(3). The total deviation I is found to be <= 0.011 au for all aromatic systems and lies between 0.011 and 0.035 au for all nonaromatic systems. For antiaromatic systems, its value is found to be above 0.035 au. Further, Sigma(3)(i=1)Delta lambda(i), gives a direct interpretation of Clar's aromatic sextet structures for PBHs. In summary, MESP topography mapping is a powerful technique to quantify the localized and delocalized pi-electron distribution in a variety of unsaturated hydrocarbon systems.