I am concentrating here on colonial and early republican statutes.
The Statutes At Large 1682 to 1809 in 18 volumes are online at the Pennsylvania Legislative Reference Bureau, in PDF format taken from the series printed from 1896 to 1915. Digitized volumes of that series can be found in the Internet Archive.
A five volume set, from 1682 to 1814, edited by Thomas Cooper, can be found in the Internet Archive. The first volume consists of ‘constitutional documents’, rather than statutes as such. Continued by a further five volumes edited by David J. McCord, much of which is organised by theme not date.
See also Grimke’s collection of Statutes up to 1790.
A transcribed version of Hening’s Statutes At Large, covering 1619 to 1792, can be found at Vagenweb.