CeNi2Al3 system is a potential candidate for low temperature thermoelectrics. Substitution studies, especially at the Ni site are considered to be of importance due to the drastic tuning of its physical properties. Resistivity in magnetic fields and thermoelectric power measurements of Cu doped CeNi2Al3 (x=0.0 to 0.4) system is reported in this investigation. This dense Kondo lattice system is investigated with an aim of understanding its basic transport mechanism. Negative magnetoresistance is seen for x=0.3 and 0.4 in the  magnetic field up to 14 T. Deviation from the Kondo behavior occurs at temperatures close to 2 K with a down turn in  resistivity. The nature of resistivity at low temperatures is investigated in view of the possible evidence for Fermi liquid behavior and also the formation of heavy Fermion in corroboration with specific heat studies. Doping dependence of linear diffusion coefficient and Sommerfeld coefficient of specific heat are analyzed and discussed in connection with the heavy Fermion formation. The results obtained show a promising trend in tuning these materials by way of Kondo route as well as by the substitution especially at the Ni site in the present system.