A series of new palladacycloalkanes of formula cis-[PdL 2 (CH 2 ) n ] (9. n=6, L=PPh 3 ; 10. n=6, L 2 =dppe; 11. n=8, L=PPh 3 ; 12. n=8, L 2 =dppe) have been prepared by two routes. In the first route, the precursor bis(1-alkenyl) complexes cis-[PdL 2 ((CH 2 ) n CHCH 2 ) 2 ] (1. n=2, L=PPh 3 , 2. n=2, L 2 =dppe, 3. n=3, L=PPh 3 , 4. n=3, L 2 =dppe) were allowed to react with Grubb’s 2nd generation catalyst to give the palladacycloalkenes, cis-[PdL 2 (CH 2 ) n CHCH(CH 2 ) n ] (5. n=2, L=PPh 3 , 6. n=2, L 2 =dppe, 7. n=3, L=PPh 3 , 8. n=3, L 2 =dppe), which were then hydrogenated to the palladacycloalkanes, 9–12. In the second route, the di-Grignard reagents BrMg(CH 2 ) n MgBr (n=6, 8) were reacted with the palladium complex [PdCl 2 (COD)] followed by immediate ligand displacement to form the respective palladacycloalkanes 10 and 12. The complexes obtained were characterized by a range of spectroscopic and analytical techniques. Thermal decomposition studies were carried out on the palladacycloalkanes 9–12 and the main organic products shown to be 1-alkenes and 2-alkenes.