In this paper, we introduce a new theoretical framework built upon fractional Sobolev-type spaces involving Riemann-Liouville (RL) fractional integrals/derivatives, which is naturally arisen from exact representations of Chebyshev expansion coefficients, for optimal error estimates of Chebyshev approximations to functions with limited regularity. The essential pieces of the puzzle for the error analysis include (i) fractional integration by parts (under the weakest possible conditions), and (ii) generalised Gegenbauer functions of fractional degree (GGF-Fs): a new family of special functions with notable fractional calculus properties. Under this framework, we are able to estimate the optimal decay rate of Chebyshev expansion coefficients for a large class of functions with interior and endpoint singularities, which are deemed suboptimal or complicated to characterize in existing literature. We can then derive optimal error estimates for spectral expansions and the related Chebyshev interpolation and quadrature measured in various norms, and also improve the available results in usual Sobolev spaces of integer regularity exponentials in several senses. As a by-product, this study results in some analytically perspicuous formulas particularly on GGF-Fs, which are potentially useful in spectral algorithms. The idea and analysis techniques can be extended to general Jacobi spectral approximations.2000 Mathematics Subject Classification. 41A10, 41A25, 41A50, 65N35, 65M60.