The electrical potential energy of a system of charges is equal to the work that must be done to assemble the system.
Let us assemble the system one by one.
1)Bring the charge - q1 from infinity to the specified point.
2)No work done till now as no force is acting on the charge.
3)Now bring the second particle -q2 from infinty and try to push it towards the other charge.
4)As there is repulsion between the two charges we have to do POSITIVE work on the system.
5)This posotive work stores POSITIVE POTENTIAL ENERGY in the system.
6)This energy is given by :-q2V = [ (-q2)(-q1)/4
r ] =q1q2/4
r