The effect of substitution of 'Hg' at the Bi-site in Bi1.7V8O16 on the phase formation and electrical properties has been studied. In Bi1.7-xHgxV8O16, single phase formation is achieved only for x <= 0.4 and all the phases crystallize in tetragonal structure. The dc electrical resistivity studies indicate that all the mercury substituted single phase compounds Bi1.7-xHgxV8O!6 are electrically semiconducting and the room temperature resistivity values increase with increasing mercury content. Alkali metals like lithium and sodium have been inserted successfully into the tunnels of Bi1.7V8O16. The lithium intercalated phase Li2.7Bi1.7V8O16 shows anti ferro magnetic ordering, whereas the sodium intercalated phase NaBi1.7V8O16 exhibits Pauli paramagnetic like behavior down to 4.5 K. (c) 2005 Published by Elsevier B.V.