Spherical Coordinates Representation

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I just wanted to know what the set of all points in which spherical coordinates can be shown in more than one way is? I think it is only the origin but I am not sure

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Depends on what exactly you definition of spherical coordinates look like, but in the usual case this set includes all points on the $z$-axis.

Every point on the $z$-axis is defined by the distance $r$ from the orign and the angel between the $z$-axis and the $xy$-plane which is equal to $-\pi/2$ or $\pi/2$ in this case. Now you can chose whatever you want for the second angel but you will stay at the same point.