a) Formally, a space of random variables can be considered as a vector space. It is then possible to define an inner product in that space, in different ways. OneOne common choicechoice is to define it as the covariance: $$ \langle X, Y \rangle = \mathrm{cov} (X, Y) = \E [ (X - \E[X]) (Y - \E[Y]) ]. $$ Since the correlation of two random variables is zero exactly if the covariance is zero, according to this definition uncorrelatedness is the same as orthogonality. (Another possibility is to define the inner product of random variables simply as the expectancy of the productexpectancy of the product.)
b) Not all the variables we consider in statisticsvariables we consider in statistics are random variables. Especially in linear regression, we have independent variables which are not considered random but predefined. Independent variables are usually given as sequences of numbers, for which orthogonality is naturally defined by the dot product (see above). We can then investigate the statistical consequences of regression models where the independent variables are or are not orthogonal. In this context, orthogonality does not have a specifically statistical definition, and even more: it does not apply to random variables.